Use of polymeric reaction product

ABSTRACT

A reaction product (A) which can be prepared by reaction, under free radical conditions, of at least one monomer (a) capable of free radical reaction, in the presence of at least one free radical initiator and of a radical of the formula (III)                  
 
where R 1  to R 3 , in each case independently of one another, are hydrogen, methyl or a radical-stabilizing and/or bulky group selected from an unsubstituted or substituted, linear or branched alkyl of two or more carbon atoms, cycloalkyl, alcohol, ether, polyether, amine, aralkyl radical, a substituted or unsubstituted aromatic, heterocyclic or olefinic hydrocarbon, a halogen atom, a substituted or unsubstituted, linear or branched alkenyl or alkynyl group, —C(O)R 5 , —C(O)OR 5 , —CR 5 R 6 —O—R 7 , —O—C(O)R 5 , —CN, —O—CN, —S—CN, —O—C═NR 5 , —S—C═NR 5 , —O—CR 5 R 6 —CR 7 R 8 NR 9 R 10 , —N═C═O, —C═NR 5 , —CR 5 R 6 -Hal, —C(S)R 5 , —CR 5 R 6 —P(O)R 7 R 8 , —CR 5 R 6 —PR 7 R 8 , —CR 5 R 6 —NR 7 R 8 , —CR 5 R 6 (OR 7 )(OR 8 ), —CR 5 R 6 (OR 7 )(NR 8 ), —CR 5 R 6 (NR 7 )(NR 8 ), an anhydride, acetal or ketal group, —SO 2 R 5 , an amidine group, —NR 5 C(S)NR 6 , —NR 5 C(S)—OR 6 , —N═C═S, —NO 2 , —C═N—OH, —N(R 5 )═NR 6 , —PR 5 R 6 R 7 , —OSiR 5 R 6 R 7  or —SiR 5 R 6 R 7 , where R 5  to R 10 , independently of one another in each case, are defined in the same way as R 1  to R 4 , or two of the radicals R 1  to R 4  form a C 4 - to C 7 -ring which in turn may be substituted or unsubstituted and, if required, may contain one or more heteroatoms, with the proviso that at least two of the radicals R 1  to R 3  are a radical-stabilizing and/or bulky group as defined above, has various uses.

The present invention relates to various uses of a reaction product (A)which was prepared by reaction, under free radical conditions, of atleast one monomer (a), capable of free radical reaction, in the presenceof at least one free radical initiator and of a radical of the formula(III), as defined below.

The technical field of the present invention is the use of reactionproducts or polymers which were prepared by free radical polymerizationin many applications in various technical fields, such as inkjet inks,cosmetics, coating materials and engineering materials.

The reaction products (A) or polymers (B) used within the scope of thepresent invention are known per se or form the subject of a parallelapplication of the Applicant.

In this context, reference may be made to DE 198 58 708.2 and the priorart cited therein. The preparation of the polymers used according to theinvention has moreover been the subject of numerous scientificinvestigations.

A free radical chain polymerization or copolymerization with anω-unsaturated oligo(methyl methacrylate) with ethyl acrylate, styrene,methyl methacrylate, acrylonitrile and vinyl acetate as copolymers isdescribed in a scientific article in J. Macromol. Sci. Chem. A 23 (7)(1986), 839–852.

Furthermore, free radical chain polymerizations and copolymerizationsusing 1,2-(trimethylsilyloxy)tetraphenylethane are described inMacromol. Chem. Phys. 201 (2000), 74–83, methyl methacrylate, styrene,phenyl acetate, butyl acrylate and glycidyl methacrylate being used asmonomers there.

An overview of free radical chain polymerizations using in particulartetraphenylethane (derivatives) is given by Otsu and Matsumoto inAdvances in Polymer Science 136, 75–137, and in Polymer Bulletin 16(1986), 95–102.

Furthermore, Harwood et al. in Macromol. Symp. 111 (1996), 25–35 reporton NMR investigations into random, block and graft copolymers usingNMR-sensitive initiators and macroinitiators. Inter alia, the reactionof a methyl methacrylate/stilbene mixture and the properties of thepolymer resulting therefrom are described there.

The abovementioned scientific papers are concerned exclusively with thereaction mechanism on which free radical chain polymerization is basedor relate to investigations into the structure of the resultingproducts. Possible uses of the reaction products or polymers discussedtherein are not mentioned.

It is an object of the present invention to demonstrate the numerouspotential uses of such specific reaction products or polymers preparedby free radical chain polymerization. The reaction products and polymersdescribed herein are of considerable interest since the chosen method ofpreparation makes it possible to establish the properties of theseproducts in a specific manner with regard to the wide range of potentialuses, in particular by the preparation of block structures by means offree radical polymerization.

In the context of the present invention, a block copolymer is understoodas meaning a polymer which has at least two polymer blocks characterizedby different monomer compositions. In the context of the presentinvention, different monomer compositions is understood as meaning thatat least two regions of the block copolymer have different monomercompositions. In the context of the present invention, it is possiblefor the transition between two blocks to be continuous, i.e., for thereto exist between two blocks a zone which has a random or regularsequence of the monomers constituting the blocks. In the context of thepresent invention, however, it is also envisaged that the transitionbetween two blocks is essentially discontinuous. An essentiallydiscontinuous transition is understood as meaning a transition zonewhich has a substantially shorter length than at least one of the blocksseparated by the transition zone. It is possible for a block to be basedonly on one type of monomer. However, it is also envisaged that a blockis composed of two or more monomers. In a preferred embodiment of thepresent invention, the chain length of such a transition zone is lessthan 1/10, preferably less than 1/20, of the block length of at leastone of the blocks separated by the transition zone.

In the context of the present invention different monomer compositionsis furthermore understood as meaning that the monomers constituting therespective block differ in at least one feature, for example in theirlinkage to one another, in their conformation or in their constitution.If, as described above, a block is composed of more than one type ofmonomer, in the present context different blocks of the block copolymercan, for example, also differ by having different concentrations of themonomers constituting a block in each case. In the context of thepresent invention, block copolymers preferably used are those which haveat least two blocks whose monomer compositions differ at least in theconstitution of the monomers.

We have found that the abovementioned and further objects are achievedby the use of a reaction product (A) which can be prepared by means of aprocess comprising the following stage (i):

-   -   (i) Reaction, under free radical conditions, of a reaction        mixture comprising at least one monomer (a), capable of free        radical reaction, in the presence of at least one radical of the        formula (III)        where R₁ to R₃, in each case independently of one another, are        hydrogen, methyl or a radical-stabilizing and/or bulky group        selected from an unsubstituted or substituted, linear or        branched alkyl of two or more carbon atoms, cycloalkyl, alcohol,        ether, polyether, amine, aralkyl radical, a substituted or        unsubstituted aromatic, heterocyclic or olefinic hydrocarbon, a        halogen atom (Hal), a substituted or unsubstituted, linear or        branched alkenyl or alkynyl group, —C(O)R₅, —C(O)OR₅,        —CR₅R₆—O—R₇, —O—C(O)R₅, —CN, —O—CN, —S—CN, —O—C═NR₅, —S—C═NR₅,        —O—CR₅R₆—CR₇R₈NR₉R₁₀, —N═C═O, —C═NR₅, —CR₅R₆-Hal, —C(S)R₅,        —CR₅R₆—P(O)R₇R₈, —CR₅R₆—PR₇R₈, —CR₅R₆—NR₇R₈, —CR₅R₆(OR₇)(OR₈),        —CR₅R₆(OR₇)(NR₈), —CR₅R₆(NR₇)(NR₈), an anhydride, acetal or        ketal group, —SO₂R₅, an amidine group, —NR₅C(S)NR₆,        —NR₅C(S)—OR₆, —N═C═S, —NO₂, —C═N—OH, —N(R₅)═NR₆, —PR₅R₆R₇,        —OSiR₅R₆R₇ or —SiR₅R₆R₇, where R₅ to R₁₀, independently of one        another in each case, are defined in the same way as R₁ to R₄,        or two of the radicals R₁ to R₄ form a C₄- to C₇-ring which in        turn may be substituted or unsubstituted and, if required, may        contain one or more heteroatoms,        with the proviso that    -   at least two of the radicals R₁ to R₃ are a radical-stabilizing        and/or bulky group as defined above,        -   as a component in coating materials,        -   in finishes and coating materials,        -   as a component in toners,        -   as a component in cosmetics,        -   as a component in resin material,        -   as a component in retention aids for papermaking,        -   as a component in solubilizers in pharmaceutical and            cosmetic formulations,        -   as incrustation inhibitors and/or soil-release polymers in            detergents,        -   as a component in filtration assistants and for protecting            and clarifying beverages,        -   as a component in disinfectants,        -   as a component in elastomeric binders,        -   in printing plates,        -   as a dispersant, preferably in inkjet pigment formulations,        -   as an assistant in a tablet matrix,        -   as an assistant in the plasticizing of concrete,        -   as biodegradable polymers for, for example, materials for            implants, surgical suture materials and garbage bags,        -   as a component in wallpaper adhesive,        -   as a component of plastics used in automotive construction,            in the household sector, for leisure articles, in the            production of road signs, window profiles, lamp covers,            garden furniture, boats, surfboards, toys, in the packaging            sector, in the production of massage apparatuses and            housings therefor, in the production of medical equipment,            in the production of equipment for information processing            and transmission, in the production of extensive wall            elements, in transport containers, in        -   housings for electrical equipment, in moldings for the            construction sector or in grating covers, and            the use of a polymer (B) which can be prepared by a process            comprising the stage (ii):    -   (ii) Reaction of the reaction product (A) obtained in stage (i),        under free radical conditions, in the presence of at least one        monomer (b) capable of free radical homopolymerization or        copolymerization,        -   as a component in coating materials,        -   in finishes and coating materials,        -   as a component in toners,        -   as a component in cosmetics,        -   as a component in resin material,        -   as a component in retention aids for papermaking,        -   as a component in solubilizers in pharmaceutical and            cosmetic formulations,        -   as a component in incrustation inhibitors and/or            soil-release polymers in detergents,        -   as a component in filtration assistants and for protecting            and clarifying beverages,        -   as a component in disinfectants,        -   as a component in elastomeric binders,        -   in printing plates,        -   as a dispersant, preferably in inkjet pigment formulations,        -   as an assistant in a tablet matrix,        -   as an assistant in the plasticizing of concrete,        -   as biodegradable polymers for, for example, materials for            implants, surgical suture materials and garbage bags,        -   as a component in wallpaper adhesive,        -   as a component of plastics used in automotive construction,            in the household sector, for leisure articles, in the            production of road signs, window profiles, lamp covers,            garden furniture, boats, surfboards, toys, in the packaging            sector, in the production of massage apparatuses and            housings therefor, in the production of medical equipment,            in the production of equipment for information processing            and transmission, in the production of extensive wall            elements, in transport containers, in housings for            electrical equipment, in moldings for the construction            sector or in grating covers.

Preferably, the radical of the formula (III) is derived from at leastone compound of the formula (I)

-   -   where R₁ to R₄, in each case independently of one another, are        hydrogen, methyl or a radical-stabilizing and/or bulky group        selected from an unsubstituted or substituted, linear or        branched alkyl of two or more carbon atoms, cycloalkyl, alcohol,        ether, polyether, amine, aralkyl radical, a substituted or        unsubstituted aromatic, heterocyclic or olefinic hydrocarbon, a        halogen atom, a substituted or unsubstituted, linear or branched        alkenyl or alkynyl group, —C(O)R₅, —C(O)OR₅, —CR₅R₆—O—R₇,        —O—C(O)R₅, —CN, —O—CN, —S—CN, —O—C═NR₅, —S—C═NR₅,        —O—CR₅R₆—CR₇R₈NR₉R₁₀, —N═C═O, —C═NR₅, —CR₅R₆-Hal, —C(S)R₅,        —CR₅R₆—P(O)R₇R₈, —CR₅R₆—PR₇R₈, —CR₅R₆—NR₇R₈, —CR₅R₆(OR₇)(OR₈),        —CR₅R₆(OR₇)(NR₈), —CR₅R₆(NR₇)(NR₈), an anhydride, acetal or        ketal group, —SO₂R₅, an amidine group, —NR₅C(S)NR₆,        —NR₅C(S)—OR₆, —N═C═S, —NO₂, —C═N—OH, —N(R₅)═NR₆, —PR₅R₆R₇,        —OSiR₅R₆R₇ or —SiR₅R₆R₇, where R₅ to R₁₀, independently of one        another in each case, are defined in the same way as R₁ to R₄,        or two of the radicals R₁ to R₄ form a C₄- to C₇-ring which in        turn may be substituted or unsubstituted,        with the proviso that    -   at least two of the radicals R₁ to R₄ are a radical-stabilizing        and/or bulky group, as defined above, or diphenylethylene,        dinaphthylethylene, 4,4′-vinylidenebis(N,N′-dimethylaniline),        4,4′-vinylidenebis(aminobenzene) or cis- or trans-stilbene,        and/or    -   from at least one compound of the formula (II)        where R₁ to R₄ and R₁₁ and R₁₂, in each case independently of        one another, are hydrogen, methyl or a radical-stabilizing        and/or bulky group selected from an unsubstituted or        substituted, linear or branched alkyl of two or more carbon        atoms, cycloalkyl, alcohol, ether, polyether, amine, aralkyl        radical, a substituted or unsubstituted aromatic, heterocyclic        or olefinic hydrocarbon, a halogen atom, a substituted or        unsubstituted, linear or branched alkenyl or alkynyl group,        —C(O)R₅, —C(O)OR₅, —CR₅R₆—O—R₇, —O—C(O)R₅, —CN, —O—CN, —S—CN,        —O—C═NR₅, —S—C═NR₅, —O—CR₅R₆—CR₇R₈NR₉R₁₀, —N═C═O, —C═NR₅,        —CR₅R₆-Hal, —C(S)R₅, —CR₅R₆—P(O)R₇R₈, —CR₅R₆—PR₇R₈,        —CR₅R₆—NR₇R₈, —CR₅R₆(OR₇)(OR₈), —CR₅R₆(OR₇)(NR₈),        —CR₅R₆(NR₇)(NR₈), an anhydride, acetal or ketal group, —SO₂R₅,        an amidine group, —NR₅C(S)NR₆, —NR₅C(S)—OR₆, —N═C═S, —NO₂,        —C═N—OH, —N(R₅)═NR₆, —PR₅R₆R₇, —OSiR₅R₆R₇ or —SiR₅R₆R₇, where R₅        to R₁₀, independently of one another in each case, are defined        in the same way as R₁ to R₄, or two of the radicals R₁ to R₄        form a C₄- to C₇-ring which in turn may be substituted or        unsubstituted and, if required, may contain one or more        heteroatoms,        with the proviso that    -   at least two of R₁ to R₄ are a radical-stabilizing and/or bulky        group, as defined above.

In the preparation of the reaction product (A) used according to theinvention and/or of the polymer (B), all monomers capable of freeradical reaction can be used as monomer (a).

It is of course also possible to use mixtures of different monomers asmonomers (a) in the context of the present invention.

According to the abovementioned process, it is also possible topolymerize mixtures of at least one hydrophilic monomer and at least onehydrophobic monomer.

Specific examples of monomers (a) are:

-   -   Dienes, such as butadiene, isoprene, myrcene, pentadienes, and        furthermore C₁- to C₂₀-alkyl and hydroxyalkyl esters of        monoethylenically unsaturated C₃- to C₁₀-monocarboxylic acids or        C₄- to C₈-dicarboxylic acids, for example methyl methacrylate,        ethyl methacrylate, propyl methacrylate (all isomers), butyl        methacrylate (all isomers), 2-ethylhexyl methacrylate, isobornyl        methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate        (all isomers), butyl acrylate (all isomers), 2-ethylhexyl        acrylate, isobornyl acrylate, benzyl acrylate, phenyl acrylate,        stearyl acrylate, diethyl maleate, hydroxyethyl acrylate,        hydroxypropyl acrylate, hydroxybutyl acrylate, furthermore        (meth)acrylates of alkoxylated C₁- to C₁₈-alcohols which have        been reacted with from 2 to 50 mol of ethylene oxide, propylene        oxide, butylene oxide and mixtures thereof; benzyl methacrylate,        phenyl methacrylate, stearyl methacrylate, methacrylonitrile,        styrene, α-methylstyrene, acrylonitrile, functionalized        methacrylates; acrylates and styrenes selected from glycidyl        methacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl        methacrylate (all isomers), hydroxybutyl methacrylate (all        isomers), cyclohexyl methacrylate, cyclohexyl acrylate, hexyl        methacrylate and hexyl acrylate (in each case all isomers),        diethylaminoethyl methacrylate, triethylene glycol methacrylate,        itaconic anhydride, itaconic acid, glycidyl acrylate,        2-hydroxyethyl methacrylate, diethylaminoethyl acrylate,        triethylene glycol acrylate, methacrylamide,        N-tert-butylmethacrylamide, N-n-butylmethacrylamide,        N-methylolmethacrylamide, N-ethylolmethacrylamide,        N-tert-butylacrylamide, N-butylacrylamide, N-methylolacrylamide,        N-ethylolacrylamide, vinylbenzoic acid (all isomers),        diethylaminostyrene (all isomers), α-methylvinylbenzoic acid        (all isomers), diethylamino-α-methylstyrene (all isomers),        p-methylstyrene, p-vinylbenzenesulfonic acid,        trimethoxysilylpropyl methacrylate, triethoxysilylpropyl        methacrylate, tributoxysilylpropyl methacrylate,        triethoxy-methylsilyipropyl methacrylate,        dibutoxymethylsilylpropyl methacrylate,        diisopropoxynethylsilylpropyl methacrylate, dimethoxysilylpropyl        methacrylate, diethoxysilylpropyl methacrylate,        dibutoxysilylpropyl methacrylate, diisopropoxysilylpropyl        methacrylate, trimethoxysilylpropyl acrylate,        triethoxysilylpropyl acrylate, tributoxysilylpropyl acrylate,        dimethoxymethylsilylpropyl acrylate, diethoxymethylsilylpropyl        acrylate, dibutoxymethylsilylpropyl acrylate,        diisopropoxymethylsilylpropyl acrylate, dimethoxysilylpropyl        acrylate, diethoxysilylpropyl acrylate, dibutoxysilylpropyl        acrylate, diisopropoxysilylpropyl acrylate, vinyl acetate and        vinyl butyrate, vinyl chloride, vinyl fluoride, vinyl bromide,        vinyl alcohol, vinyl ethers of C₁- to C₁₈-alcohols, vinyl ethers        of alkoxylated C₁- to C₁₈-alcohols and vinyl ethers of        polyalkylene oxides, such as polyethylene oxide, polypropylene        oxide or polybutylene oxide, monoethylenically unsaturated C₃-        to C₁₀-monocarboxylic acids, their alkali metal salts and/or        ammonium salts, for example acrylic acid, methacrylic acid,        dimethylacrylic acid, ethylacrylic acid, allylacelic acid or        vinylacetic acid, furthermore monoethylenically unsaturated C₄-        to C₈-dicarboxylic acids, their monoesters, anhydrides, alkali        metal salts and/or ammonium salts, for example maleic acid,        fumaric acid, itaconic acid, mesaconic acid, methylenemalonic        acid, citraconic acid, maleic anhydride, itaconic anhydride or        methylmalonic anhydride; furthermore monoethylenically        unsaturated monomers containing sulfo groups and their salts,        for example their alkali metal or ammonium salts, for example        allylsulfonic acid, styrenesulfonic acid,        2-acrylamido-2-methylpropanesulfonic acid (AMPS),        methallylsulfonic acid, vinylsulfonic acid, 3-sulfopropyl        acrylate or 3-sulfopropyl methacrylate, furthermore        monoethylenically unsaturated monomers containing phosphonic        acid groups or their salts, for example their alkali metal or        ammonium salts, for example vinylphosphonic acid,        allylphosphonic acid or acrylamidoethylpropanephosphonic acid,        furthermore amides and N-substituted amides of monoethylenically        unsaturated C₃- to C₁₀-monocarboxylic acids or C₄- to        C₈-dicarboxylic acids, for example acrylamide,        N-alkylacrylamides or N,N-dialkylacrylamides, each having 1 to        18 carbon atoms in the alkyl group, such as N-methylacrylamide,        N,N-dimethylacrylamide, N-tert-butylacrylamide or        N-octadecylacrylamide, N-monomethylhexylmaleamide,        N-monodecylmaleamide, diethylaminopropylmethacrylamide or        acrylamidoglycollic acid; furthermore alkylaminoalkyl        (meth)acrylates, for example dimethylaminoethyl acrylate,        dimethylaminoethyl methacrylate, ethylaminoethyl acrylate,        diethylaminoethyl methacrylate, dimethylaminopropyl acrylate or        dimethylaminopropyl methacrylate; furthermore vinyl esters, such        as vinyl formate, vinyl acetate or vinyl propionate, where these        may also be present in hydrolyzed form after the polymerization;        furthermore N-vinyl compounds, for example N-vinylpyrrolidone,        N-vinylcaprolactam, N-vinylformamide, N-vinyl-N-methylformamide,        1-vinyl-imidazole or 1-vinyl-2-methylimidazole; furthermore        vinyl ethers of C₁- to C₁₈-alcohols, vinyl ethers of alkoxylated        C₁- to C₁₈-alcohols and vinyl ethers of polyalkylene oxides,        such as polyethylene oxide, polypropylene oxide or polybutylene        oxide, styrene or its derivatives such as α-methylstyrene,        indene, dicyclopentadiene, monomers which carry amino or imino        groups, such as dimethylaminoethyl methacrylate,        diethylaminoethyl acrylate, diethylaminopropyl methacrylamide or        allylamine, monomers which carry quaternary ammonium groups, for        example present as salts, as obtained by reacting basic amino        functions with acids, such as hydrochloric acid, sulfuric acid,        nitric acid, formic acid or acetic acid, or in quaternized form        (examples of suitable quaternizing agents are dimethyl sulfate,        diethyl sulfate, methyl chloride, ethyl chloride or benzyl        chloride), e.g. dimethylaminoethyl acrylate hydrochloride,        diallyldimethylammonium chloride, dimethylaminoethyl acrylate        methylchloride, dimethylaminoethylaminopropylmethacrylamide        methosulfate, vinylpyridinium salts or 1-vinylimidazolium salts;        monomers in which the amino groups and/or ammonium groups are        liberated only after the polymerization and subsequent        hydrolysis, for example N-vinylformamide or N-vinylacetamide,        and mixtures of two or more of the abovementioned monomers.

Styrenes, acrylonitrile, (meth)acrylates or their free acid, dienes orN-vinyl compounds, preferably the members of this group which have beenmentioned above, or mixtures of two or more thereof, if required with atleast one further monomer (a) capable of free radical homopolymerizationor copolymerization, are preferably used as a first monomer (a).

According to the invention, a compound of the formula (I)

or of the formula (II)

is furthermore used in the preparation of the reaction product (A), inorder to obtain the radical of the formula (III).

Here too, in principle all compounds of the abovementioned formulae canbe used according to the invention, provided that they correspond to theabove definition or the definition given in the claims.

It is particularly important that at least two of the radicals R₁ to R₄or R₁ to R₃ in formula (III) are a radical-stabilizing and/or bulkygroup. The term bulky group as used in the context of the presentinvention means that it is a group whose dimensions in each case in thenovel reaction under free radical conditions are greater than or equalto the dimensions of an isopropyl radical. The term radical-stabilizinggroup used according to the invention denotes groups of the type definedin claim 1, whose electron structure permits stabilization of radicals.

Specific examples are the following groups of the abovementioned type:branched alkyl groups of three or more carbon atoms, in particularisopropyl and tert-butyl; cycloalkyl groups, for example unsubstitutedor substituted cyclopentyl or cyclohexyl; alcohol groups, for exampleradicals of branched alcohols, such as isopropoxy or tert-butoxy;aralkyl radicals; substituted or unsubstituted aromatic or heterocyclichydrocarbons, such as phenyl or pyridyl; halogen; cyano; nitro; estergroups of the structure —C(O)OR₅, where the radical R₅ may be, forexample, linear or branched, unsubstituted or substituted alkyl, aralkylor an aromatic or heteroaromatic group.

Other preferred compounds of the formula (I) are those which have, asradical-stabilizing groups, the following combination of groups:

-   -   at least one substituted or unsubstituted phenyl or C(O)R₅;    -   at least one substituted or unsubstituted phenyl and CN;    -   at least one substituted or unsubstituted phenyl and C(O)OR₅;    -   independently of one another, at least two substituted or        unsubstituted phenyl groups,    -   independently of one another, at least two C(O)OR₅; and    -   independently of one another, at least two CN.

In particular.

-   -   1,1,4,4-tetraphenyl 1,3-butadiene    -   1,4-bis(2-methylstyryl)benzene    -   1,2,3,4,5-pentaphenyl-1,3 -cyclopentadiene    -   1,2,3,4-tetraphenyl-1,3-cyclopentadiene    -   acenaphthylene    -   cis- and trans-alpha-methylstilbene    -   cis- and trans-4,4′-diphenylstilbene, diphenylethylene,        dinaphthylethylene, 4,4′-vinylidenebis(N,N′-dimethylaniline),        4,4′-vinylidenebis(amino-benzene), cis- and trans-stilbene,    -   trans-trans- and trans-cis- and        cis-cis-1,4-diphenyl-1,3-butadiene    -   alpha,omega-tetraphenylpolyethyne    -   diphenylfulvene    -   triphenylethene    -   tetraphenylethene    -   1-cyano-1-phenylethylene; 1-alkoxycarbonyl-1-phenylethylene;        1,1-dialkoxycarbonyl-2-ethylethylene;        1,1-dialkoxycarbonyl-2-phenylethylene,        1,1-dialkoxycarbonyl-2,2-dimethylethylene;        1,1-dialkoxycarbonylmethylethylene; 9-methylenexanthene;        9-methylenethioxanthene, 9-methylene-10-H-acridine or mixtures        of two or more thereof        are used as the compound of the formula (I) or (II).

According to the invention, the radical formation may be effected bydifferent methods. For example, thermal, photochemical, electrochemicalor electron-transfer-induced production is just as possible as the useof oxidizing or reducing agents for producing radicals.

In addition, the process described herein can be carried out in thepresence of at least one free radical initiator. Thermally,electrochemically or photochemically initiating monomers may also beused as initiators. In general, however, all azo and/or peroxo compoundsconventionally used in free radical chain polymerization and/orcompounds having homolytically cleavable C—C bonds may be used. Suitableinitiators are described, for example, on page 10, line 17 to page 11,line 15 of WO 98/01478, which is hereby fully incorporated in thecontext of the present application; in addition,3,4-dimethyl-3,4-diphenylhexane and 2,3-dimethyl-2,3-diphenylbutane maybe used. Preferably used initiators are those which are soluble in thereaction system used in each case, In the case of reaction in theaqueous phase, oxidizing free radical initiators, e.g. potassium, sodiumand ammonium peroxodisulfate, or a combination of a conventional, i.e.of a nonoxidizing, initiator with H₂O₂ are preferably used. Dicumylperoxide, dibenzoyl peroxide, dilauryl peroxide and AIBN may also beused.

In a preferred embodiment of the process a comparatively large amount offree radical initiator is added, the amount of free radical initiator asa proportion of the reaction mixture preferably being from 0.1 to 50,particularly preferably from 0.5 to 20, % by weight, based in each caseon the total amount of the monomer (a) and of the initiator. The molarratio of initiator to compound (I) is preferably from 3:1 to 1:3,particularly preferably from 2:1 to 1:2. in particular from 1.5:1 to1:1.5.

If the described reaction according to stage (i) is carried out in theaqueous phase, the term aqueous phase is understood in the context ofthe present text as meaning a phase which contains from 10 to 100% byweight of water. If the amount of water in the aqueous phase is lessthan 10%, it is preferable in the context of the present invention ifthe aqueous phase contains a mixture of water and one or morewater-miscible solvents, such as THF, methanol, ethanol, propanol,butanol, acetone, methyl ethyl ketone or the like. However, it is alsopossible to carry out the reaction according to stage (i) in thepresence of a mixture of water and a water-immiscible solvent, such asan aromatic solvent, for example toluene.

In a further embodiment, the above reaction according to stage (i) iscarried out in the presence of at least one base. The low molecularweight bases used may be in principle all low molecular weight bases,NaOH, KOH, ammonia, diethanolamine, triethanolamine, mono-, di- ortriethylamine, dimethylethanolamine or a mixture of two or more thereofbeing preferred and ammonia and di- and triethanolamine beingparticularly preferred.

However, it is also possible to carry out the reaction according tostage (i) in an organic solvent or in the absence of a solvent, forexample in the melt. When the term reaction in an organic solvent or inthe absence of a solvent is used in the context of the presentinvention, it is understood as meaning a reaction which takes place inthe presence of less than 10, preferably less than 5 or less than 1, %by weight of water. In a further embodiment of the present invention, atleast one block copolymer in whose preparation stage (i) was carried outin an organic solvent or in the absence of a solvent is used in thenovel binder composition, the water content of the reaction mixturebeing less than 0.5, for example less than 0.3 or less than 0.1, % byweight. In a further embodiment of the present invention, the reactionof stage (i) is carried out in the absence of water, i.e. with a watercontent of less than 0.001% by weight. Such water contents can beachieved, for example, by using commercially available solvents, asusually used as organic solvents in free radical polymerizations.

In the context of the present invention, suitable solvents are inprinciple all polar and nonpolar organic solvents in which thecorresponding polymers and preferably also the polymers formed aresoluble, if necessary at elevated temperature. Suitable solvents are,for example, C₃- to C₁₀-alkanes, cyclohexane, decalin, acetone, methylethyl ketone, diisobutyl ketone, tetrahydrofuran, dioxane, benzene,toluene, glycols such as ethylene glycol and triethylene glycol, glycolethers in which some or all of the terminal groups are blocked, such asethylene glycol monomethyl ether, ethyl acetate, methanol or ethanol orthe higher homologs of the alkanols of up to 18 carbon atoms (ifnecessary as cosolvent) or mixtures of two or more thereof.

The reaction according to stage (i) is generally carried out at aboveroom temperature and below the decomposition temperature of themonomers, preferably a temperature range from 50 to 200° C., furtherpreferably from 70 to 150° C., in particular from 80 to 120° C., beingchosen.

The reaction according to stage (i) is generally carried out atpressures from 1 to 300, for example from about 1.5 to 100 or from about2 to about 20, bar.

Although there are no restrictions at all regarding the molecular weightdistribution, a reaction product which has a molecular weightdistribution M_(w)/M_(n), measured by gel permeation chromatographyusing polystyrene as standard, of ≦4, preferably ≦3, further preferably≦2, in particular ≦1.5 and in specific cases also ≦1.3 can be obtainedin the reaction according to (i). The molecular weight of the reactionproduct (A) can be controlled within wide limits by the choice of theratio of monomers (a) to compounds (I) to free radical initiator. Inparticular, the content of compound (I) determines the molecular weightand does so in such a way that the larger the amount of compound (I) thelower the molecular weight obtained.

The reaction according to stage (i) can also be carried out in thepresence of a surfactant.

The reaction product obtained in the reaction according to (i) can befurther processed directly or can be used as a macroinitiator for thefurther reaction according to stage (ii), as defined further belowherein. It is also possible to isolate the reaction product according tostage (i) as a solid and then to react it further or to use it.

At least one freely selectable monomer (b) capable of free radicalhomopolymerization or copolymerization can be subjected to the reactionaccording to stage (ii), suitable monomers (b) being the monomersmentioned above in conjunction with the explanation of the monomers (a).

Monomer (b) may be identical to or different from the monomer (a) usedin stage (i). It is of course also possible to use mixtures of two ormore monomers as monomer (a) or monomer (b). The choice of the monomer(b) is made in principle according to the desired structure of thepolymer prepared in stage (ii) and hence depending on the desired use ofthis polymer.

Specific examples are the following monomers (b) preferably to be used:

-   -   Styrene and derivatives, e.g. styrenesulfonic acid, methacrylic        acid and acrylic acid, and the esters of these acids with        methanol, ethanol, propanol (all isomers), butanol (all        isomers), hexane (all isomers), vinyl acetate, hydroxyethyl        acrylate, hydroxyethyl methacrylate, N-vinyl compounds, e.g.        N-vinylpyrrolidone, and dienes, such as butadiene, isopiene,        myrcene and pentadiene.

Accordingly, the present invention also relates to a process for thepreparation of a polymer (B), which comprises:

-   -   (ii) Reaction of the reaction product (A) obtained in stage (i),        under free radical conditions, in the presence of at least one        monomer (b) capable of free radical homopolymerization or        copolymerization.

The reaction according to stage (ii) is carried out in principle underthe conventional conditions for a free radical polymerization or underthe conditions prevailing in stage (i) it being possible for suitablesolvents to be present.

In a further embodiment of the present invention, stage (ii) can becarried out in the presence of compounds of the formula I or II, whichare added after the end of stage (i).

In the process described herein, stages (i) and (ii) can be carried outseparately from one another both in terms of space and in terms of time,in which case, of course, stage (i) is carried out first, followed bystage (ii). In addition, however, stages (i) and (ii) can also becarried out in succession in one reactor, i.e. first the compound of theformula (I) is reacted completely or partially with at least one monomer(a), depending on the desired use or the desired properties, and then atleast one monomer (b) is added and is subjected to free radicalpolymerization, or a monomer mixture comprising at least one monomer (a)and at least one monomer (b) is used from the outset and is reacted withthe compound (I). It is assumed that first the compound (I) reacts withthe at least one monomer (a) and then the reaction product (A) formedtherefrom also reacts with the monomer (b) above a specific molecularweight. In this context, it should be noted in particular that the novel(co)polymerization can be continued after any interruption withoutfurther addition of initiator, by heating to a temperature at which themacroinitiator formed according to reaction product (A) decomposesagain.

The resulting polymer (reaction product (A)) can be isolated or can bereheated in situ to initiate the (further) polymerization. Furthermonomer (b) can be identical to or different from monomer (a). It isalso possible to use monomer mixtures from the outset. Stage (ii) can berepeated as often as desired, if necessary after isolation of therespective products in the individual stages.

Depending on the reaction procedure, it is possible according to theinvention to prepare polymers functionalized at the terminal groups,segmented polymers, block, multiblock or gradient (co)polymers, star(co)polymers, graft copolymers and branched and hyperbranched(co)polymers.

As is evident from the above, the present invention also relates to theuse of the polymer (B), which can be prepared by the process definedabove, for numerous applications. The reaction is preferably carried outin such a way that a polymer (B) which has a block structure isobtained. Using an easily obtainable compound (I), it is possible in asimple manner to provide block copolymers which have, for example, ahydrophilic block, e.g. a (meth)acrylic acid or a C₁₋₄-alkyl(meth)acrylate block, and a fisher, preferably hydrophobic polymerblock, e.g. a block based on vinylaromatic monomers, such as styrene orsubstituted styrenes, acrylonitrile, dienes and nonaromatic vinylcompounds, such as vinyl acetate, and higher (>C₄) alkyl(meth)acrylates.

Polymers of the following structure are preferably used:

-   -   Poly((meth)acrylic        acid-stat-(meth)acrylate-b-(styrene-stat-(meth)acrylate)), where        the term (meth)acrylate denotes alkyl esters of methacrylic acid        or acrylic acid.

Specific examples are the following block copolymers:

-   -   Poly(acrylic acid-b-styrene), poly(methyl        methacrylate-b-styrene), poly(styrene-b-vinyl acetate),        poly(methacrylic acid-b-hydroxyethyl acrylate), poly(methyl        methacrylate-b-N-vinylpyrrolidone), poly(methyl        methacrylate-b-N-vinylformamide), poly(methyl        methacrylate-b-hydroxyethyl acrylate), poly(methyl        methacrylate-b-(styrene-stat-acrylonitrile)), poly(n-butyl        acrylate-b-styrene-b-n-butyl acrylate), poly(methyl        methacrylate-b-styrene-b-methyl methacrylate-b-styrene),        poly(n-butyl acrylate-b-styrene-b-n-butyl acrylate-b-styrene),        poly((meth)acrylic        acid-stat-(meth)acrylate-b-(styrene-stat-(meth)acrylate)).

Specific examples are the following block copolymers:

-   -   Poly(styrene-b-acrylic acid), poly(styrene-b-methyl acrylate),        poly(styrene-b-ethyl acrylate), poly(styrene-b-methacrylic        acid), poly(styrene-b-methyl methacrylate), poly(styrene-b-ethyl        methacrylate), poly(hydroxyethyl acrylate-b-methacrylic acid),        poly(N-vinylpyrrolidone-b-methyl acrylate),        poly(N-vinylpyrrolidone-b-ethyl acrylate),        poly(N-vinylpyrrolidone-b-methyl methacrylate),        poly(N-vinylpyrrolidone-b-ethyl methacrylate),        poly(N-vinylpyrrolidone-b-styrene),        poly(N-vinylpyrrolidone-b-vinyl acetate),        poly(N-vinylpyrrolidone-b-(α-methylstyrene),        poly(N-vinylformamide-b-methyl methacrylate),        poly(N-vinylformamide-b-ethyl methacrylate),        poly(N-vinylformamide-b-vinyl acetate),        poly(N-vinylformamide-b-methyl acrylate) or        poly(N-vinylformamide-b-ethyl acrylate).

The following can also be prepared according to the present invention:

-   -   Poly(methyl methacrylate-b-(styrene-stat-acrylonitrile),        poly(n-butyl acrylate-b-styrene-b-n-butyl acrylate),        poly(styrene-b-n-butyl acrylate-b-styrene),        poly(styrene-b-n-butyl acrylate-b-styrene-b-n-butyl acrylate),        poly(methyl methacrylate-b-styrene-b-methyl        methacrylate-b-styrene), poly(n-butyl        acrylate-b-styrene-b-n-butyl acrylate-b-styrene),        poly(styrene-b-polybutadiene),        poly(styrene-b-styrene-stat-butadiene),        poly(styrene-stat-acrylonitrile-b-butadiene),        poly-(styrene-stat-acrylonitrile-b-styrene-stat-butadiene),        poly(styrene-stat-acrylonitrile-b-styrene-stat-acrylonitrile-stat-butadiene),        poly(styrene-b-vinylpyrrolidone),        poly(styrene-stat-acrylonitrile-vinylpyrrolidone), poly(n-butyl        acrylate-b-styrene), poly(n-butyl        acrylate-styrene-acrylonitrile) and their ABA/ABC three-block        polymers or higher block polymers and the like.

As stated at the outset, the present invention relates to the use of thereaction products (A) and/or (B) described above for improving orproviding specific properties within application products. The reactionproducts (A) and/or polymers (B) described herein (often referred tobelow as components) can be used individually or as a mixture of two ormore thereof. Furthermore, it is possible to use the components as suchor in the form of solutions, suspensions, dispersions, emulsions, solidsor engineering material, and to do so as a function of the respectivemethod of use. The novel uses are described individually in detailbelow, reference being made where possible to publications in which theuse described herein has been described in principle with the use ofother polymers or reaction products.

Use as Component of Coating Materials, in Particular in Finishes andSurface Coatings

The reaction products (A) described herein and the polymer (B) or amixture of two or more thereof can be used in the context of the presentinvention as a component of coating materials, in a form suitable forthis purpose, in particular as polymer dispersions.

In addition to said components (A) or (B), such coating materialscontain additives (C) suitable for their field of use, such as polymers,in particular crosslinking agents, crosslinking catalysts, initiators,in particular pigments, dyes, fillers, reinforcing fillers, rheologyassistants, wetting agents and dispersants, antifoams, adhesionpromoters, additives for improving substrate wetting, additives forimproving surface smoothness, dulling agents, leveling agents,film-forming assistants, drying agents, antiskinning agents, lightstabilizers, corrosion inhibitors, biocides, flameproofing agents,polymerization inhibitors, in particular photoinhibitors, orplasticizers, as are customary and known, for example, in the plasticsor leather sector. The choice of the additive depends on the desiredproperty profile of the coating material and its intended use.

These coating materials can be applied by the known methods ofapplication of liquid phases, such as dipping, spraying, knife coating,brushing, roller coating or pouring in the form of a liquid curtain.Examples of suitable substrates are films, sheets, fibers, metal sheets,woven fabrics or shaped articles, in particular automotive bodyworkcomponents, of metal, glass, wood, paper, plastics, leather, mineralsubstrates or composite materials thereof. During application, thesesubstrates may be stationary or moving, as, for example, in the coilcoating method.

Furthermore, such coating materials may be used in powder form, inparticular in powder coating.

In particular, the coating materials may be components of multilayercoat structures, as encountered, for example, in automotive OEMfinishing, automotive refinishing, plastics coating, industrial coating,container coating or the coil coating method or in furniture coating.

Use as a Component in Toners

Toner compositions can be prepared by various known methods, for exampleby mixing together and heating resin particles which contain thecomponents (A) or (B) described herein, for example correspondingstyrene/butadiene copolymers, with pigments, such as magnetite, carbonblack or mixtures thereof, and colored pigments, such as cyan, magenta,yellow, green, brown or red pigments or mixtures thereof, and preferablyfrom 0.5 to 5% by weight of an additive for increasing the charge in anextrusion apparatus for toners, for example ZSK 53 from Werner &Pfleiderer, and subsequently removing the resulting toner compositionfrom the apparatus. After cooling, the toner composition is milled in asuitable micronizing apparatus in order to obtain toner particles whichhave a mean diameter of less than about 25 μm, preferably from 6 to 12μm, these diameters being determined using a Coulter counter. This isfollowed by classification of the particles, toner particles having adiameter of less than 4 μm being removed.

Details regarding such toner compositions are disclosed, for example, inU.S. Pat. No. 5,322,912, in particular in columns 11 to 15 thereof, thecontent of which regarding the components of a toner composition arehereby fully incorporated in the context of the present application.

Use as Component in Cosmetics

Reaction products (A) or polymers (B) having film-forming properties areused in cosmetics as film formers for cosmetic, dermatological, hygieneand/or pharmaceutical formulations and are particularly suitable asadditives for hair and skin cosmetics.

In the cosmetic and dermatological formulations for the skin, the novelreaction products (A) or polymers (B) are particularly effective. Thereaction products (A) or polymers (B) can, inter alia, help to keep theskin moist and to condition it and improve the feel of the skin.

The reaction products (A) or polymers (B) are preferably used forsetting and shaping the hair and improving its structure. They increasethe combability and improve the feel of the hair. These hair treatmentagents generally contain a solution of the film former in an alcohol ora mixture of alcohol and water.

One requirement of hair treatment agents is that they impart, interalia, gloss, flexibility and a naturally pleasant feel to the hair.

In addition to the novel reaction products (A) or (B) and suitablesolvents, the cosmetic, dermatological, hygiene and/or pharmaceuticalformulations can also contain conventional additives, such asemulsifiers, preservatives, perfume oils, cosmetic active ingredients,such as phytantriol, vitamins and provitamins, for example vitamin A, Eand C, retinol, bisabolol, panthenol, natural and synthetic lightstabilizers, natural substances, propellants, solubilizers, repellents,bleaches, coloring compositions, toning compositions, tanningcompositions (for example dihydroxyacetone), micropigments, such astitanium oxide or zinc oxide, reflectors, proteins, for example wheat,almond or pea proteins, ceramide, pH-α-hydroxy acids, fruit acids,collagen, protein hydrolysis products, stabilizers, pH regulators,colors, salts, thickeners, gel formers, consistency regulators,silicones, humectants, natural oil replenishers and further conventionaladditives.

Preferably, the novel reaction products (A) or polymers (B) are used asor in coating material(s) for keratin-containing and keratin-analogoussurfaces, such as hair, skin and nails.

In the formulation of hair setting compositions, it should be borne inmind that a reduction of the alcohol and propellant content is requiredowing to the environmental provisions for controlling the emission ofvolatile organic compounds (VOC) into the atmosphere.

Particularly suitable reaction products (A) or polymers (B) are thosewhich are water-soluble or whose water dispersibility is so high thatthey are soluble in a 20:80 (V%/V%) water/ethanol solvent mixture in anamount of more than 0.1, preferably more than 0.2, g/l.

For example, the novel reaction products (A) or polymers (B) are used incosmetic compositions for cleansing the skin. Such cosmetic cleansingcompositions are selected from bar soaps, such as toilet soaps, curdsoaps, transparent soaps, luxury soaps, deodorant soaps, cream soaps,baby soaps, skin protection soaps, abrasive soaps and syndets, liquidsoaps, such as pasty soaps, soft soaps and wash pastes, and liquidwashing, shower and bath preparations, such as wash lotions, showercompositions and gels, foam baths, oil baths and scrub preparations andshaving foams, lotions and creams.

They are particularly suitable for hair cosmetics, preferably informulations such as hair repair treatments, hair lotions, hair rinses,hair emulsions, split end fluids, neutralizing compositions forpermanent waves, hot-oil treatment preparations, conditioners, settinglotions, shampoos, hair dyes or hair sprays.

The skin care compositions are present in particular as W/O or O/W skincreams, day and night creams, eye creams, face creams, antiwrinklecreams, moisturizing creams, bleaching creams, vitamin creams, skinlotions, care lotions and moisturizing lotions.

Depending on the field of use, the cosmetic, hygiene, dermatologicaland/or pharmaceutical formulations can be applied as spray (pump sprayor aerosol), foam, gel, gel spray, lotion or mousse.

They are furthermore suitable for skin cosmetic formulations, such asface lotions, face masks, deodorants and other cosmetic lotions, and foruse in decorative cosmetics, for example as a masking pen, theaterpaint, in mascara and eye shadow, lipsticks, kajal sticks, eyeliners,rouges, powders and eyebrow pencils.

The novel reaction products (A) or polymers (B) can also be used in nosestrips for pore cleansing, in antiacne compositions, repellents, shavingcomposites, depilatories, feminine hygiene compositions and foot carecompositions and in baby care.

Furthermore, the novel reaction products (A) or polymers (B) aresuitable as excipients in pharmacy, preferably as or in coatingcomposition(s) or binder(s) for solid dosage forms. They can also beused in creams and as tablet coating compositions and tablet binders.

The novel reaction products (A) or polymers (B) are contained in thecosmetic, dermatological or hygiene formulations in an amount of fromabout 0.001 to 20, preferably from 0.1 to 10, % by weight, based on thetotal weight of the composition.

Examples of particularly suitable solvents are water and lowermonoalcohols or polyols of 1 to 6 carbon atoms and mixtures thereof,preferred monoalcohols or polyols are ethanol, isopropanol, propyleneglycol, glycerol and sorbitol.

Further additives which may be present are fatty substances, such asmineral and synthetic oils, for example paraffins, silicone oils andaliphatic hydrocarbons of more than 8 carbon atoms, animal and vegetableoils, for example sunflower oil, coconut oil, avocado oil, olive oil,lanolin or waxes, fatty acids, fatty esters, for example triglyceridesof C₆- to C₃₀-fatty acids, wax esters, such as jojoba oil, fattyalcohols, vaseline and hydrogenated lanolin. Mixtures thereof can ofcourse also be used.

Conventional thickeners in such formulations are crosslinked polyacrylicacid and its derivatives, polysaccharides, such as xanthan gum, agaragar, alginates or tyloses, cellulose derivatives, for examplecarboxymethylcellulose or hydroxycarboxymethylcellulose, fatty alcohols,monoglycerides and fatty acids, polyvinyl alcohol andpolyvinylpyrrolidone.

After the polymerization of the novel reaction products (A) or polymers(B), other polymers can also be admixed if specific properties are to beestablished.

Examples of conventional polymers suitable for this purpose are anionic,cationic, amphoteric and neutral polymers.

Use as Resin Material

Regarding the use of components (A) and (B) described herein as resinmaterial, reference is made to DE-A 196 36 058, which describes astyrene resin material. It is of course also possible to prepare otherresin materials, for example polymers based on acrylic acid/butadieneand acrylic acid/styrene or acrylic acid/styrene/acrylic acid orcopolymers of styrene and acrylonitrile in the same or an analogousmanner. Such resin materials are described below using a styrene resinmaterial as an example.

According to the invention, the (co)polymers can be mixed with at leastone ether monomer. For example, the polymers described in EP-B 0 512951, in particular on page 4, line 6 to page 5, line 33, are suitablefor this purpose.

If desired, the resin material may contain lubricants, antistaticagents, antioxidants, heat stabilizers, ultraviolet absorbers, pigments,dyes, nucleating agents, rubbers, fillers, dulling agents, brighteningcompositions, flameproofing agents, blowing agents, mold release agentsand the additives and plasticizers, such as mineral oil, which arementioned in WO 97/27233, page 5, line 1 to page 5, line 37 and in EP-B0 512 95 1, page 6, lines 6–21 and page 7, lines 23–41.

According to the invention, the polymers stated in the presentapplication are used for processing to give moldings, sheets, fibers andfoams. The rheological and thermal behavior is critical for theperformance characteristics and processing properties. To ensure as faras possible trouble-free processing, it is important to keep the meltviscosity low, so that the polymers mentioned here, which have a lowviscosity, are particularly suitable.

Before they are processed to give moldings, sheets, fibers and foams,the polymers arc generally mixed with additives which are useful formodifying the basic properties (modifiers, plasticizers, fillers andreinforcing materials, flameproofing agents, antistatic agents, dyes,pigments, etc.) or for carrying out the processing in a trouble-freemanner (stabilizers, lubricants, mold release agents, etc.). The novelpolymers used can also be employed as a mixture with other polymers,such as polyethylene terephthalate (PET), polybutylene terephthalate(PBT), polycarbonate (PC), polyamide (PA 6), polyamide 66 (PA 66),polyamide 12 (PA 12), polyamide 4,6 (PA 4,6), copolyamides,polypropylene oxide (PPO), polyetherimides, polyetherketones,polyimides, acrylonitrile/butadiene/styrene (polymers) (ABS),acrylonitrile/styrene/acrylate (polymers) (ASA), poly(amidoimides),polybutadiene, poly(meth)acrylate, epoxy resins, polyethylene (PE),polypropylene (PP), EPDM (ethylenepropylenediene monomer rubber),copolymers of α-olefins, polyvinyl chloride (PVC), polymethylmethacrylate (PMMA), polystyrene (PS), styrene/acrylonitrile copolymers(SAN), polyvinyl alcohol, polyvinyl acetate, thermoplastic polyurethaneelastomers (TPU), polylactide, and polymers described in chapter 5 ofPolymer Handbook, 3rd ed., Brandrup, J. and Immergut, E H, published byJohn Wiley & Sons, 1989, New York, and their blends and copolymers andblock copolymers. Further suitable additives and polymers are known tothose skilled in the art.

a) Compounding

The additives and further polymers are generally introduced with thepolymer mentioned here by compounding prior to processing, and thestarting materials are converted into a form ready for processing.Suitable compounding methods are mixing, if required subsequentroll-milling and kneading (plasticization) and, if required, subsequentgranulation.

b) Processing

The moldings, sheets, fibers and foams can be produced by variousmethods. In general, the polymers mentioned according to the presentapplication can be processed by means of any conventional method to givemoldings, sheets, fibers and foams. Suitable methods are describedbelow.

Processing Methods at Atmospheric Pressure

Processing methods at atmospheric pressure which are suitable, forexample, for processing low-viscosity melts are casting, for examplemonomer casting and film casting, dipping, for example paste dipping,brushing and expansion.

Processing Under Pressure

In processing under pressure, a melt is first produced by the action ofheat and is then molded and is set by cooling. Suitable processingmethods under pressure are pressing as well as rolling and calendering,multistage roll mills with additional apparatuses being required forshaping (melt rolling method, calendering), extrusion, by means ofwhich, for example, continuous semifinished products, such as pipes,tubes, profiles, sheets, films, wire sheets, monofils, etc. and, afterthe extrusion process, hollow articles can be produced, and blow moldingmethods for the production of closed hollow articles (e.g. toys), orhollow articles open at one end (e.g. bottles, containers) from tubularparisons, for example the abovementioned extrusion blow molding methodand injection blow molding method. A further important processing methodunder pressure is injection molding, which permits the production of amultiplicity of complicated shapes.

The processing is preferably carried out by extrusion, blow molding andinjection molding, particularly preferably by injection molding.

In the processing of polymers by extrusion or blow molding, it isadvantageous if the polymers used have a low shear viscosity in themelt, i.e. the shear viscosity of the polymers during the melting in theextruder at high temperatures is low. In comparison, the shear viscosityat lower temperatures, when the molding material leaves the extruder,should be of the conventional order of magnitude.

During the processing of the polymers mentioned in the presentapplication by injection molding, it is advantageous that the polymershave a low viscosity in the melt.

c) Forming

The processing can, if required, be followed by a forming method. Thenon-cutting forming of semifinished products by the application ofexternal forces and heat serves for increasing the strength or forchanging the shape. Suitable forming methods are, for example,orientation (stretching) and heat setting, e.g., deep drawing, by meansof which semifinished products can be converted into sheets and tiles.The forming is preferably carried out by deep drawing.

Use as Retention Aid for Papermaking

The components (A) and (B) described herein can also be used asretention aids in the production of all paper grades and cardboards. Inthis context, reference is made to DE 197 19 059 and the paper gradesand cardboards described therein.

These components are preferably suitable for use in the production ofpaper from sulfite or sulfate pulp in the bleached or unbleached state,it being possible for this fiber material to contain up to 100% byweight of groundwood and/or waste paper and therefore to have a highproportion of mineral fillers, pigments and fibrous crill.

The components (A) and (B) are added to the paper stock dispersion in anamount of from 0.1 to 10, preferably from 0.5 to 5, particularlypreferably from 1.0 to 3, % by weight, based on the dry solids content,upstream of the head box of the paper machine. The addition is made tothe dispersion which may contain or to which has been added, as fillers,calcium carbonate, kaolin, aluminum silicate and hydrated aluminumoxides, satin white, talc, gypsum, barite, calcium silicate andlithopone, kieselguhr and synthetic, organic fillers from the recycledmaterial.

The components (A) and (B) are advantageously added to the stockdispersion in the headbox, upstream of the vertical screen and upstreamor downstream of the stock pump, prior to sheet formation.

By using the components (A) and (B), excellent retention of the fillersis achieved and surprisingly impairment of the strength values isavoided in spite of the increase in the filler and hence in the ashcontent of the paper. This is particularly true for the use of stockdispersions which contain waste paper or mechanical pulps, such asgroundwood and thermomechanical pulp (TMP), or consist thereof

It was also found that, by using the components (A) and (B), the effectof optical brighteners, which are added to improve the whiteness of thepaper stock, is not adversely affected.

Use as Solubilizer in Pharmaceutical and Cosmetic Formulations

The components (A) and (B) described herein can also be used assolubilizers in pharmaceutical and cosmetic formulations.

Pharmaceutical and cosmetic formulations can be obtained by processingthe components (A) and/or (B) with pharmaceutical or cosmetic activeingredients by conventional methods and with the use of known activeingredients.

The pharmaceutical or cosmetic active ingredients used are substanceswhich are is sparingly soluble in water and have a water solubility of10 g/l or less. The active ingredients may be from any area ofindications. Examples here are benzodiazepines, antihypertensive drugs,vitamins, cytostatic drugs, anaesthetics, neuroleptic drugs,antidepressants, antibiotics, antimycotic drugs, fungicides,chemotherapeutic drugs, urological drugs, platelet aggregationinhibitors, sulfonamides, spasmolytic drugs, hormones, immunoglobulins,sera, thyroid therapeutics, psychotropic drugs, antiparkinson drugs andother antihyperkinetic drugs, ophthalmic drugs, neuropathicpreparations, calcium metabolism regulators, muscle relaxants,narcotics, lipid depressants, hepathotherapeutic drugs, coronary drugs,cardiac drugs, immunotherapeutic drugs, regulatory peptides and theirinhibitors, hypnotics, sedatives, gynecological drugs, gout remedies,fibrinolytic drugs, enzyme preparations and transport proteins, enzymeinhibitors, emetics, drugs for stimulating blood flow, diuretics,diagnostic agents, corticoids, cholinergics, drugs for treatment of thebiliary ducts, antihistamines, broncholytics, beta receptor blockers,calcium antagonists, ACE inhibitors, arteriosclerotic drugs,antiphlogistic drugs, anticoagulants, antihypotensive drugs,antihypoglycemic drugs, antihypertensive drugs, antifibrinolytic drugs,antiepileptic drugs, antiemetics, antidotes, antidiabetic drugs,antiarrhythmic drugs, antianemic drugs, antiallergic drugs,anthelmintics, analgesics, analeptic drugs, aldosterone antagonists andslimming preparations.

The novel compounds are used as solubilizers in a known manner Forexample, the active ingredient is mixed with them and water is added, ifrequired with gentle heating, or the novel compounds are dissolved inwater, if required with gentle heating, with simultaneous or subsequentaddition of active ingredient.

Use as Incrustation Inhibitor and/or Soil Release Polymers in Detergents

The components (A) and/or (B) described herein, preferably copolymers ofthe type described above which have been rendered hydrophobic, can alsobe used as incrustation inhibitors and/or soil release polymers indetergents. Regarding the general formulation of such detergents and thefunction as incrustation inhibitor and/or soil release polymer,reference may be made to DE-A 196 08 044.

The components (A) and/or (B), preferably in a form renderedhydrophobic, are used as incrustation-inhibiting additives in amountsfrom 0.01 to 20% by weight in detergent powders. Their proportion of thetextile detergent powders is generally from 0.05 to 15% by weight.

Cleaning agents are to be understood as meaning, for example, cleanersfor hard surfaces, for example for metal, plastics, glass and ceramiccleaning, floor cleaners, sanitary cleaners, general-purpose cleaners inthe household and in commercial applications, industrial cleaners (foruse in car washes or high-pressure cleaners), cold cleaners, dishwashingagents, rinse aids, disinfectant cleaners, cleaners for the food andbeverage industry, in particular as bottle cleaners, as CIP cleaners(cleaning-in-place) in dairies, breweries and other facilities of foodmanufacturers. Cleaners which contain the polymerization mixtures to beused according to the invention are particularly suitable for cleaninghard surfaces, such as glass, plastics and metal. The cleaners may bealkaline, acidic or neutral. They usually contain surfactants in amountsfrom about 0,2 to 50% by weight. These may be anionic, nonionic orcationic surfactants or mixtures of surfactants which are compatiblewith one another, for example mixtures of anionic and nonionic or ofcationic and nonionic surfactants. Alkaline cleaners may contain sodiumcarbonate, potassium carbonate, sodium bicarbonate, potassiumbicarbonate, sodium sesquicarbonate, potassium sesquicarbonate, sodiumhydroxide, potassium hydroxide, amine bases, such as monoethanolamine,diethanolamine, triethanolamine or ammonia, or silicate in amounts of upto 60% by weight and in some cases even up to 80% by weight. Thecleaners may furthermore contain citrates, gluconates or tartrates, inamounts of up to 80% by weight. They may be present in solid or liquidform.

The components (A) and/or (B) to be used according to the invention maybe considered as cobuilders. Since they significantly reduce theincrustation during the washing of textiles, they may also be referredto as incrustation inhibitors. The detergents may be present in powderform or as a liquid formulation. The composition of the detergents andcleaning agents may be very different. Washing and cleaning formulationsusually contain from 2 to 50% by weight of surfactant and, if required,builders. These data apply both to liquid detergents and to detergentpowders. Detergent and cleaning agent formulations which are commonlyused in Europe, the USA and in Japan are listed, for example, in a tablein Chemical and Engn. News, 67 (1989), 35. Further data on thecomposition of detergents and cleaning agents can be obtained fromUllmanns Enzyklopädie der technischen Chemie, Verlag Chemie, Weinheim1983, 4th edition, pages 63 to 160.

Reduced-phosphate detergents are to be understood as meaning thoseformulations which contain not more than 25% by weight of phosphate,calculated as pentasodium triphosphate. The detergents may be heavy-dutydetergents or special detergents. Suitable surfactants are both anionicand nonionic surfactants and mixtures of anionic and nonionicsurfactants. The surfactant content of the detergents is preferably from8 to 30% by weight.

The surfactants present may be both anionic and nonionic surfactants,reference being made to the abovementioned DE-A 196 08 044 with regardto individual anionic and/or nonionic surfactants which may be used.

In addition, the detergents in powder or granular form and possibly alsostructured liquid detergents contain further components customary indetergents, for example one or more inorganic builders, bleaches, enzymesystems, soil release polymers and/or antiredeposition inhibitors,reference likewise being made to DE-A 196 08 044 in this context forfurther details on these components.

In connection with soil release polymers, it should be mentioned herethat the polymers (B) described herein are also particularly suitableowing to the possibilities of modifying them in a virtually freelyselectable manner with regard to their properties in the preparationprocess described here. For example, it is preferable to use inparticular amphiphilic graft polymers or copolymers as described herein,amphiphilic graft polymers or copolymers of vinyl esters and/oracrylates on polyalkylene oxides being mentioned in particular.

Use as Filtration Aid, for Clarifying Beverages

The components (A) and/or (B) described herein can also be used asfiltration aids and for clarifying beverages. In this context, referencemay be made to EP-B 0 351 363, the content of which is herebyincorporated in full by reference in the context of the presentspecification. In this context, reference may be made in particular tothe section from column [lacuna], line 10 to column 6, line 29 of thispublication.

It is particularly advantageous to meter the filtration aid, i.e. thecomponents (A) and (B) described herein, continuously into theunfiltered material. This can be realized in particular by metering inone operation or by metering in the crossflow circulation. It isadvantageous if the stabilizer is pumped with the circulation ofunfiltered material through the membrane filter of the crossflowfiltration unit. The circulation may be closed directly from the outletof the filtration unit via a pump back to the inlet thereof. However, itis also possible to close the circulation via the working tank, i.e. topump the unfiltered material continuously from the working tank throughthe membrane filter and to transport the retentate present at the outletof the filtration unit, together with the stabilizer contained therein,back into the working tank. Owing to the small pore size of suchcrossflow membrane filters (from 0.001 to 1 μm in the case ofultrafiltration or from about 0.1 to 1 μm in the case ofmicrofiltration), the entry of bound or precipitated tannins or proteinsinto the filtrate is reliably prevented. Instead, these are circulatedwith the retentate on the unfiltered material side of the membranefilter until the end of a filtration cycle.

The filtration aid may be metered in without recovery and removed fromthe filtration unit together with the sediments after the end of afiltration cycle. Polyvinylpolypyrrolidone (PVPP) and further blockcopolymers described herein and silica gel have proven particularlyuseful.

If the unfiltered material contains large amounts of suspended matter,the filtration performance of the membrane filters can be increased ifgranular or fibrous filtration aids are fed to the membranes forprotecting the membrane pores from blockage by sediments

Granular is understood as describing those filtration aids which consistof regularly or irregularly shaped particles which neither dissolve inthe unfiltered material nor agglomerate or are otherwise compacted underthe influence of the transmembrane pressure. According to the invention,filtration aids consisting of such granular particles are deposited inspite of the crossflow along the membrane surface and can thus preventthe formation of continuous top layers of sediments.

The filtration aid can advantageously be applied as a top layer directlyon the membrane surface. Consequently, the pores of the membrane surfaceare reliably protected from blockage by sediments. The top layer shouldhave a layer thickness of 1 to 20 μm, preferably from 1 to 8 μm; ittherefore does not constitute a filter layer in the conventional sensebut a protective layer for the actual membrane filter layer.

The filtration aid can be applied to the membrane surface before thebeginning of the filtration process. This produces a top layer whichconsists exclusively of the filtration aid and is free of contaminationby sediments. This can be achieved if first a medium which contains nosubstantial amounts of suspended matter is caused to flow across themembrane in order to start up a filtration cycle, if filtration aid isadded to the medium in order to form the top layer and if the unfilteredmaterial is then fed to the membrane. Such a top layer can be easilyproduced if the filtration cycle is started up with water to whichfiltration aid is added. As soon as the top layer has been produced, thewater can be forced out of the filter as a forward flow and unfilteredmaterial can be fed in.

In many applications, it may be advantageous if the filtration aid isadded to the unfiltered material. If, owing to the suspended matterpresent in the unfiltered material, there is no pronounced tendency torapid formation of top layers comprising sediment, the filtration cyclecan be started up in this way. A top layer of the filtration aid thenforms, in which certain amounts of sediment are incorporated.Alternatively, however, it is also possible, after the formation of atop layer comprising filtration aid, also to add filtration aidcontinuously or batchwise to the unfiltered material after the startupwith water or filtrate. The particles of the filtration aid disturb anysediment layers so that they become more permeable. Moreover, thegranular filtration aid prevents the formation of compact layers, sothat the crossflow can more readily dissolve sediment deposits.

The protection of the membrane pores from blockage is ensured in aparticularly reliable manner if filtration aid having a particle sizewhich is greater than the pore size of the filter membrane is applied. Aparticle size of from 1 to 80 μm has proven particularly useful, and, byan appropriate choice of the particle size distribution, for examplefrom 60 to 80% of the particles in the range from 1 to 4 μm, it ispossible to optimize the filtration aid in this range with respect tothe medium to be filtered and the suspended matter contained therein,Particularly good permeability and a large filtration surface can beachieved if kieselguhr is used as filtration aid.

Regarding further details, reference may be made to EP-B 0 351 363, asstated above.

Use as Components in Disinfectants

Regarding this use, reference may be made herein to EP-A 0 756 820,which relates to the use of dextrins in disinfectants. However, thesedextrins alone are not capable of forming sufficiently stable iodinecomplexes. Surprisingly, however, they can do so when mixed with thereaction products (A) or the polymers (B) described herein, since thesecopolymers are likewise capable of taking up iodine, and are able to doso with a bond force comparable to that of dextrin, for examplehomopolyvinylpyrrolidones and block copolymers of N-vinylpyrrolidone andstyrene, methyl methacrylate, methyl acrylate, hydroxymethyl acrylate orhydroxyethyl acrylate.

The disinfectants resulting therefrom have improved stability andconsequently also improved properties with respect to the disinfectantaction.

The formulations can be used in the form of ointments, solutions,shampoos, creams, soaps, gels or suppositories and in gelatin capsules,gargling solutions, sprays or sticks, such as lipsticks. Formulationshaving a pH of from 1 to 8, preferably from 2 to 7 and particularlypreferably from 3 to 6, are preferred.

According to the invention, it is also possible to prepare tablets of adextrin-containing iodophor. A particular advantage of this is that,surprisingly, the iodophor, in contrast to known iodophors, is directlytabletable, i.e. can be compressed into tablets without further tabletbinders. In this way, binder-free iodophor tablets can be obtained in asimple and economical manner. If desired, small amounts of additives,such as lubricants, for example polyethylene glycols or fatty acidsalts, such as magnesium stearate, can also be incorporated into thetablets, as can disintegrants, for example crospovidone.

Effervescent tablets comprising dextrin-containing iodophor and alkalimetal and/or alkaline earth metal bicarbonates or carbonates areparticularly advantageous. Because the tablet floats, the activesubstance can be more uniformly distributed in the water withoutstirring being necessary. This is particularly advantageous ifrelatively large amounts of water are to be treated, for example indrinking water treatment or in fish farming.

The dextrin-containing iodophors can also be processed to give pelletsor granules without binders having to be added.

The tablets, pellets or granules can also be prepared assustained-release preparations having coats which dissolve slowly.

The formulations are suitable in particular for use in the coarsedisinfection of surfaces as well as fine disinfections. Thus, they canbe used in compositions for the antiseptic treatment of skin and mucousmembranes or for disinfecting hands for surgical and hygiene purposes.

The novel formulations are furthermore suitable for the preparation ofcompositions for the treatment of skin disorders, such as decubitus,varicose ulcers, dermatomycoses, pyodermia, acne and vaginitis, and forthe treatment of burn wounds.

Furthermore, the novel formulations can be used in the area ofveterinary medicine, for example for disinfecting equipment, for udderdisinfection, in fish breeding, for example for disinfection of fisheggs, for disinfecting animal sheds, especially in chicken rearing, inparticular in egg laying. They are also suitable for the preparation ofdrugs for the treatment of diarrhea in animals.

Particularly when used in veterinary medicine or in animal breeding, itis advantageous to use tablets, granules or pellets. These forms aremore readily meterable than powders, avoid dust contamination and can beadministered directly or can be simply mixed with feed.

Use as Elastomeric Binders in Printing Plates

In this context, reference may be made to DE 2980246.8.

Examples of suitable elastomeric binders are elastomeric polymericbinders, for example polyalkadienes, vinylaromatic/alkadiene copolymersand block polymers, alkadiene/acrylonitrile copolymers,ethylene/propylene copolymers, ethylene/propylene/alkadiene copolymers,ethylene/acrylic acid copolymers, alkadiene/acrylic acid copolymers,alkadiene/acrylate/ acrylic acid copolymers and ethylene/(meth)acrylicacid/(meth)acrylate copolymers, in each case prepared as describedabove.

Elastomers which contain conjugated alkadienes, such as butadiene orisoprene, and styrene are very particularly suitable. The elastomericbinder is contained in the photopolymerizable cylinder layer in anamount of from 50 to 95, preferably from 50 to 90, % by weight based onthe total amount of the components contained in the cylinder layer.

Furthermore, the photopolymerizable relief-forming cylinder layer usedaccording to the invention contains conventional and knowncopolymerizable ethylenically unsaturated organic compounds which arecompatible with the polymeric binder, in an amount from 1 to 60,advantageously from 2 to 50, in particular from 3 to 40, % by weight,based on the total amount of the cylinder layer. The term compatibleindicates that the relevant monomers are miscible with the elastomericbinder so readily that no haze or waviness is produced in the relevantphotopolymerizable relief-forming cylinder layer. Examples of suitablemonomers are the conventional and known acrylates and methacrylates ofmonohydric and polyhydric alcohols, acrylamides and methacrylamides,vinyl ethers and vinyl esters, allyl ethers and allyl esters anddiesters of fumaric acid or of maleic acid, in particular the esters ofacrylic and/or methacrylic acid with monohydric or preferably polyhydricalcohols, for example esters of acrylic or methacrylic acid withethanediol, propanediol, butanediol, hexanediol, oxaalkanediols, forexample diethylene glycol, or esters of acrylic or methacrylic acid withtrihydric or polyhydric alcohols, such as glycerol, trimethylolpropane,pentaerythritol or sorbitol, for example. Examples of particularlysuitable mono- and polyfunctional acrylates or methacrylates are butylacrylate, butyl methacrylate, 2-ethylhexyl acrylate, lauryl(meth)acrylate, hexanediol diacrylate, hexanediol dimethacrylate,ethylene glycol di(meth)acrylate, butanediol 1,4-di(meth)acrylate,neopentylglycol di(meth)acrylate, 3-methylpentanediol di(meth)acrylate,2-hydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate,1,1,1-trimethylolpropane tri(meth)acrylate, di-, tri- and tetraethyleneglycol di(meth)acrylate, tripropylene glycol di(meth)acrylate orpentaerythrityl tetra(meth)acrylate, and furthermore poly(ethyleneoxide) di(meth)acrylate, ω-methylpoly(ethyleneoxide)-α-yl-(meth)acrylate, N,N-diethylaminoethyl acrylate, a reactionproduct of 1 mol of glycerol, 1 mol of epichlorohydrin and 3 mol ofacrylic acid, and glycidyl methacrylate and bisphenol A diglycidyl etheracrylate.

Mixtures of photopolymerizable ethylenically unsaturated organiccompounds and, for example, mixtures of monofunctional (meth)acrylates,such as hydroxyethyl methacrylate, with polyfunctional (meth)acrylatesof the abovementioned type are also suitable.

In addition to the (meth)acrylates, derivatives of (meth)acrylamides,for example N-methylol(meth)acrylamidoethers of polyols (for exampleglycol), are also suitable.

In addition to the elastomeric binder and copolymerizable ethylenicallyunsaturated monomeric compounds the cylinder layer crosslinkable byactinic radiation (=photosensitive recording layer) contains one or morephotoinitiators, for example benzoin or benzoin derivatives, such asbenzoin ethers of straight-chain or branched monoalcohols of 1 to 6carbon atoms, for example benzoin methyl, ethyl, isopropyl, n-butyl orisobutyl ether, symmetrically or asymmetrically substituted benzilacetals, such as benzil dimethyl acetal, benzil 1-methyl 1-ethyl acetal,diarylphosphine oxides, such as 2,4,6-trimethylbenzoyldiphenylphosphineoxide or 2,6-dimethoxybenzoyldiphenylphosphine oxide oracyldiarylphosphine oxides according to German Laid-Open ApplicationDE-OS 2,909,992, or hydroxypropanones, such as1-phenyl-2-methyl-2-hydroxy-1-propanone and 1-hydroxycyclohexyl phenylketone. They may be used alone or as a mixture with one another or incombination with coinitiators, for example benzoin methyl ether withtriphenylphosphine, diacylphosphine oxides with tertiary amines oracyldiarylphosphine oxides with benzil dimethyl acetal.

In the mixtures they are used in an amount from 0.001 to 10,advantageously from 0.1 to 5, in particular from 0.3 to 2, % by weight,based on the total amount of the photosensitive cylinder layer, theamount being determined by, inter alia, the presence ofphotopolymerizable monomers.

Thermal polymerization inhibitors which have no significantself-absorption in the actinic range in which the photoinitiator absorbscan be added as further assistants which may be present, in general inan amount from 0.001 to 2% by weight, based on the total amount of thephotosensitive cylinder layer, for example 2,6-di-tert-butyl-p-cresol,hydroquinone, p-methoxyphenol, β-naphthol, phenothiazine, pyridine,nitrobenzene, m-dinitrobenzene or chloranil; thiazine dyes, such asthionine blue G (C.I. 52025), methylene blue B (C.I. 52015) or toluidineblue (C.I. 52040); or N-nitrosamines, such as N,N-nitrosodiphenylamine,or the salts, for example the potassium, calcium or aluminum salts, ofN-nitrosocyclohexylhydroxylamine.

Suitable dyes, pigments or photochromic additives may also be added tothe photosensitive mixture of the recording layer, in an amount from0.0001 to 2% by weight, based on the mixture.

The preparation of the photopolymerizable relief-forming cylinder layerused according to the invention from its components is carried out ingeneral by mixing the components with the aid of known mixing methods orby processing the mixture for the IR-sensitive layer with the aid ofknown techniques, such as casting from solution, calendering orextrusion, it also being possible for these measures to be combined withone another in a suitable manner.

The cylinder layer crosslinkable by actinic radiation generally has athickness of from 200 to 8000 μm, in particular from 500 to 6000 μm. Afurther thin layer which may have a thickness of from 1 to 5 μm andwhich detackifies the surface of the photosensitive cylinder layer maybe applied thereon. Present on the latter or preferably directly on thecylinder layer crosslinkable by actinic radiation is the IR-sensitivelayer, which is a layer which is soluble or dispersible in developersand contains, in a film-forming binder having elastomeric character, atleast one finely divided substance which has high absorption in thewavelength range from 750 to 20,000 nm and an optical density ≧2.5 inthe actinic range. Developers may be water and water/alcohol or organicsolvent (mixtures). Suitable binders having elastomeric character forthe IR-sensitive layer are polymers, in particular copolymers, which areeither water-soluble or dispersible in water or water/alcohol mixturesor those which are soluble or dispersible in organic solvents or solventmixtures. Suitable alcohols in the water/alcohol mixtures are methanol,ethanol, n-propanol and isopropanol.

Examples of binders which are soluble or dispersible in water or inwater/alcohol mixtures and have elastomeric character are polyvinylalcohol/polyethylene glycol graft copolymers (for example Mowiol® 597from Hoechst Aktiengesellschaft, Germany), which are obtainable bygrafting vinyl acetate onto polyehtylene glycol having molecular weightsof from 1000 to 50,000 and then carrying out hydrolysis to a degree ofhydrolysis of from 90 to 100%.

Examples of binders which are soluble or dispersible in organic solventsor solvent mixtures and have elastomeric character are thermoplasticpolyamide resins which can be prepared, for example, by conventionalpolycondensation and are marketed, for example, under the nameMacromelt® by Henkel KGaA, Germany. All of the abovementioned productsare described in detail in the respective relevant company publications.

The film-forming binders having elastomeric character and present in theIR-sensitive layer contain finely divided substances which have a highabsorption in the IR range. Examples of such substances are variousfinely divided carbon black grades, for example pigment black FW2000,special black 5, Printex® U from Degussa Aktiengesellschaft, Germany,having a mean primary particle size of from 13 to 30 nm. Advantageouslyused solutions are those which contain binders having elastomericcharacter and substances having high IR absorption, which solutions areeither applied uniformly and directly onto the cylinder layer and driedor cast to give a film, dried and laminated with the cylinder layer. Thefilm can, if required, be peeled off.

It is also possible to apply a peelable film transparent to actiniclight, a cover sheet which has a thickness of from 5 to 300 μm, whichconsists, for example, of polyethylene or polyethylene terephthalate, tothe IR-sensitive layer.

Synthetic oligomers or resins, such as oligostyrene, oligomericstyrene/butadiene copolymers, oligomeric α-methylstyrene/p-methylstyrenecopolymers, liquid oligobutadienes, liquid oligoisoprenes or liquidoligomeric acrylonitrile/butadiene copolymers, each prepared asdescribed above, may also be used. Such oligomers are molecules having amolecular weight of from 500 to 5000 g/mol.

Use as Dispersants, Preferably as Dispersants in Inkjet PigmentFormulations

The components (A) and (B) described here are extremely useful for thepreparation of aqueous dispersions and perform the function of adispersant. In this context, reference may be made to DE-A 100 05 648.

If components (A) and (B) are used as dispersants, then, for example,aqueous dispersions which have excellent long-term stability can beobtained therefrom. Depending on the intended use of the dispersionsthus obtainable, the amount of these components in the total aqueousdispersion can vary within wide ranges. If the components are used, forexample, as dispersants for stabilizing a dispersion which contains asolid which is not self-dispersible, the amount of the novel compoundsused may be from about 0.01 to about 40, for example from about 0.1 toabout 20 or from about 0.5 to about 10 or from about 1 to about 5, % byweight. The amount of solids in such a dispersion can vary over a widerange. Depending on the intended use, it is therefore possible to usethe novel compounds to obtain dispersions which have a solids content ofup to about 99% by weight. Particularly when such dispersions are to beused for coating surfaces, they preferably have a solids content of fromabout 30 to about 95, for example from about 40 to about 90 or fromabout 50 to about 80, % by weight.

The present invention therefore also relates to aqueous dispersions, atleast containing one of the components (A) and (B).

In a further preferred embodiment, however, these components are alsosuitable as the sole component of such a dispersion, in particular asthe disperse phase of an aqueous dispersion. Such dispersions can beused, for example, as coating materials for the production of surfacecoatings. When used in this manner, it is advantageous if the componentused is a compound which, after removal of the continuous phase, gives asurface coating which corresponds to the user's requirements. When usedin this manner, it is therefore preferable, according to the invention,if the novel compound used is a compound having a molecular weight of atleast about 1000.

In addition to water and one of the components, or a mixture of two ormore thereof, the novel aqueous dispersions may also contain one or morefurther compounds.

If the novel aqueous dispersion is to be used as a surface coatingmaterial, the dispersion may contain, for example, at least one polymerwhich is obtainable by polymerization of monomers having ethylenicallyunsaturated double bonds. Suitable monomers are, for example, acrylicacid, methacrylic acid, acrylonitrile, acrylates or methacrylates, asobtainable by esterifying acrylic acid or methacrylic acid withmethanol, ethanol, n-butanol, isobutanol, or 2-ethylhexyl alcohol, vinylesters of carboxylic acids of 1 to 16 carbon atoms or 1-alkenes, such asethylene, propylene or butylene, or styrene. Such polymers may, forexample, already be in dispersed or at least polymerized form when mixedwith the novel dispersion. However, it is also possible to prepare saidpolymers in the novel aqueous dispersion. Here, the respective compoundsand reaction conditions can be chosen so that, for example, at least apart of the polymers produced in the dispersion are added, by means of agrafting reaction, to the novel compounds present in the dispersion.Corresponding polymers are prepared by methods known to those skilled inthe art, as described, for example, in D. C. Blackley, EmulsionPolymerization—Theory and Practice, London, Applied Science Publishers,1975, or in H. Warson, Application of Synthetic Resin Emulsions, London,Benn Publishers, 1972, or in I. Piirma, Emulsion Polymerization, NewYork, Academic Press Inc., 1982.

The novel dispersions may furthermore contain additives, such as organicsolvents, pigments, dyes, emulsifiers, surfactants, thickeners,stabilizers, leveling agents, fillers, sedimentation inhibitors,flameproofing agents, UV stabilizers or antioxidants.

Suitable solvents are, for example, acetone, methyl ethyl ketone,tetrahydrofuran, dimethylformamide, dimethylacetamide, dioxane, ethylacetate and the like, or a mixture of two or more thereof. The noveldispersions may contain the organic solvents in an amount of up to about20, preferably up to about 10, % by weight.

Other suitable thickeners in addition to the novel components (A) and(B) themselves are polymers of hydrophilic monomers capable of freeradical polymerization, such as acrylic acid or methacrylic acid,polyvinylpyrrolidone or thickeners based on cellulose or starchderivatives, such as carboxymethylcellulose, carboxyethylcelluse,hydroxyethylcellulose, hydroxypropylcellulose, hydroxyethyl starch,hydroxypropyl starch and the like, Said thickeners may each be presentindividually or as a mixture of two or more thereof in the noveldispersions.

Suitable fillers or pigments are, for example, titanium dioxide,antimony oxide, zinc oxide, basic lead carbonate, basic lead sulfate,barium carbonate, porcelain powder, clay, aluminum silicate, silica,magnesium carbonate, magnesium silicate or calcium carbonate. Forexample, cadmium yellow, cadmium red, carbon black, phthalocyanine blue,chromium yellow, toluidyl red and hydrated iron oxide may be used ascolored pigments.

The novel dispersions are prepared by generally customary methods knownto those skilled in the art. Suitable methods are described, forexample, in Kunststoffhandbuch, No. 7, Polyurethane, Carl Hanser Verlag,1993.

The novel aqueous dispersions can be used in particular as surfacecoating materials. In this respect, they may be combined with amultiplicity of substrates. Examples of suitable substrates are wood,metal, glass, textiles, leather, paper, plastics and the like. The novelaqueous dispersions can be applied by any desired, conventional methods,such as dipping, spraying, knife coating, brush application or the like.

The present invention furthermore relates to the use of at least one ofthe components (A) and (B) as wetting agents, dispersants, surfactants,adhesion promoters, assistants in electroplating baths, acid catalystsin chemical syntheses or curing components in coating materials.

The novel polymeric dispersants, as an individual substance or as amixture, are particularly suitable for wetting, dispersing andstabilizing pigments in aqueous or solvent-containing suspensions. Ithas been found that the novel dispersants lead to good fixing of thepigments on, in particular, cellulosic fibers, which is confirmed byexcellent wet and dry abrasion resistances. The pigments can be selectedfrom among colored pigments or magnetic pigments.

Regarding this use, reference may be made to DE-A 19842952.5, which ishereby fully incorporated by reference in the context of the presentapplication.

This publication also lists, for example, suitable pigments, such asmonoazo pigments, diazo pigments, vat dyes, inorganic pigments andmagnetic pigments.

Expediently, the pigments are first converted with the novel dispersantinto a suitable form for use, a pigment formulation. The pigmentformulations can be used directly, for example as print paste or ink, orcan be used for the preparation of a form for use, for example a writingink or inkjet ink. The pigment formulations can be incorporated intoaqueous or organic systems simply and without undesirable flocculation.For the preparation of the pigment formulations, the pigments are mixedwith the novel dispersants and, if desired, further additives in thepresence of a diluent, such as water. For liquid preparation, in whichthe pigment is finely distributed in the presence of relatively largeamounts of diluent, in particular dissolvers for predispersing andstirred ball mills are suitable, such as bead mills generally and thosehaving small grinding beads (having, for example, a diameter of 0.3 mm),such as the double-cylinder bead mills (DCP-Super Flow®) fromDraiswerken GmbH, Mannheim, or the centrifugal fluidized-bed mills (ZWM)from Netzsch Gerätebau GmbH, Selb. In this way, finely divided andlow-viscosity pigment formulations are obtained. Compared withconventional dispersants, the novel dispersant leads to advantageouslyhigh flowabilities and stable storage behavior. When pigmentformulations prepared using the novel dispersant were stored, nosettling of the pigment was observed over months.

Moreover, the novel dispersant can be used universally for amultiplicity of different pigments.

Alternatively, the pigment can be processed with the dispersant, with orwithout heating, to give a plastic material. Mixers and plasticatingapparatuses, such as kneaders, extruders and/or roll mills, areparticularly suitable for this purpose.

The pigment contained in the pigment formulation after dispersing shouldbe very finely divided. Preferably 95%, particularly preferably 99%, ofpigment particles have a particle size of <1 μm, preferably <5 μm.

The novel pigment formulations contain, as a rule, from 0.1 to 35,preferably from 0.1 to 20, particularly preferably from 0.2 to 10, % byweight of pigment.

Water is the main component of the novel pigment formulations. Itscontent is as a rule from 35 to 90, preferably from 45 to 80, % byweight.

The novel pigment formulations preferably also contain a humectant,reference once again being made here to DE-A 19842952.5 with regard toexamples of such humectants. Suitable humectants in addition topolyhydric alcohols, in particular of 3 to 8 carbon atoms, such asglycerol, erythritol or pentaerythritol, are pentitols, such asarabitol, adonitol and xylitol, and hexitols, such as sorbitol, mannitoland dulcitol, especially polyalkylene glycols and polyalkylene glycolmonoalkyl ethers, which are also to be understood as meaning the lower(di-, tri- and tetra-)alkylene glycols and alkylene glycol ethers. Thesecompounds preferably have average molecular weights of from 100 to 1500,polyethylene glycols and polyethylene glycol ethers having an averagemolecular weight of <800 being particularly preferred.

Of course, the novel pigment formulations may contain furtherassistants, as are customary in particular for (aqueous) inkjet inks andin the printing and coatings industry. Examples which may be mentionedare preservatives (such as 1,2-benzoisothiazolin-3-one and its alkalimetal salts, glutardialdehyde and/or tetramethylolethyleneurea),antioxidants, degassers/antifoams (such as acetylenediols andethoxylated acetylenediols, which usually contain from 20 to 40 mol ofethylene oxide per mole of acetylenediol and at the same time have adispersant effect, or phosphoric acid/alcohol mixtures), compositionsfor regulating the viscosity, leveling agents, wetting agents,antisettling agents, gloss improvers, lubricants, adhesion improvers,antiskinning compositions, dulling agents, emulsifiers, stabilizers,water repellents, light-stabilizing additives, handle improvers andantistatic agents. If these compositions are components of the novelpigment formulations, their total amount is as a rule ≦1% by weight,based on the weight of the formulation.

The novel pigment formulations usually have a dynamic viscosity of from1 to 20, preferably from 1 to 5, mm²/sec.

The surface tension of the novel pigment formulations is as a rule from20 to 70, preferably from 35 to 60, mN/m.

The pH of the novel pigment formulations is in general from 5 to 11,preferably from 7 to 9.

In the preparation of the novel pigment formulations, it is expedient toproceed as follows:

The pigment, for example in the form of a water-containing press cake orin the form of a dry pigment powder, is mixed together with one or morenovel dispersant(s) in the presence of water and predispersed in asuitable apparatus. The mixture obtained is then milled in a mill inorder to establish the desired pigment particle size distribution, afterwhich further assistants are added. Finally, the final formulation isprepared by adding corresponding amounts of water and, if required, oneor more humectants and, if required, further assistants, mixing and thenfixing by means of a filtration apparatus with fines removal in therange from, as a rule, 10 to 1 μm and preferably then by means of afurther filtration apparatus with fines removal in the range from 1 to0.5 μm.

The novel pigment formulations can advantageously be used in thelikewise novel process for the printing of sheet-like orthree-dimensional substrates by the inkjet printing method, wherein thepigment formulations are printed onto the substrate and the printobtained is then fixed.

In the inkjet method, usually aqueous inks in small droplets are sprayeddirectly onto the substrate. A distinction is made between a continuousmethod in which the ink is forced uniformly through a nozzle and isguided by an electric field, depending on the pattern to be printed,onto the substrate, and an interrupted inkjet or drop-on-demand methodin which the ink is ejected only where a colored dot is to bepositioned. In the last-mentioned method, pressure is exerted on the inksystem either by means of a piezoelectric crystal or by means of aheated cannula (bubblejet or thermojet method) and an ink droplet isthus forced out. Such procedures are described in Text. Chem. Color,Volume 19 (88), pages 23 to 29, 1987, and Volume 21 (6), pages 27 to 32,1989.

The novel pigment formulations are particularly suitable as inks for thebubblejet method and for the method by means of a piezoelectric crystal.

The novel pigment formulations can be printed on all types of substratematerials. Examples of substrate materials which may be mentioned are

-   -   cellulose-containing materials, such as paper, board, cardboard,        wood and woodbase materials, which may also have been treated        with a finish or otherwise coated,    -   metallic materials, such as foils, sheets or workpieces made of        aluminum, iron, copper, silver, gold, zinc or alloys of these        metals, which may have been treated with a finish or otherwise        coated,    -   silicate materials, such as glass, porcelain and ceramic, which        may likewise have been coated,    -   polymeric materials of any type, such as polystyrene,        polyamides, polyesters, polyethylene, polypropylene, melamine        resins, polyacrylates, polyacrylonitrile, polyurethanes,        polycarbonates, polyvinyl chloride, polyvinyl alcohols,        polyvinyl acetates, polyvinylpyrrolidones and corresponding        copolymers and block copolymers, biodegradable polymers and        natural polymers, such as gelatin,    -   textile materials, such as fibers, yarns, thread, knits, wovens,        nonwovens and ready-made goods composed of polyester, modified        polyester, polyester blend fabrics, cellulose-containing        materials, such as cotton, cotton blend fabrics, jute, flax,        hemp and ramie, viscose, wool, silk, polyamide, polyamide blend        fabrics, polyacrylonitrile, triacetate, acetate, polycarbonate,        polypropylene, polyvinyl chloride, polyester microfibers and        glass fiber fabric,    -   leather, both natural and artificial, in the form of smooth        leather, nappa leather or suede leather,    -   food and cosmetics.

The substrate material may be sheet-like or three-dimensional and may beprinted with the novel pigment formulations both uniformly andimagewise.

The novel pigment formulations are extremely useful for the productionof writing inks and of toners, in particular of aqueous, liquid toners,and of toner powders.

The toners can be produced, for example, conventionally by mixing,kneading, milling and screening pigments with the polymeric dispersants.

Use as Excipients in a Tablet Matrix

The components (A) and (B) described herein are also suitable forformulating active ingredients for drugs, crop protection agents, feedsand foods and also feed supplements and food supplements, fragrances andperfume oils, where the proportion by weight of said components in thefinal formulation may be from 1 to 99% by weight. It is of course alsopossible to use mixtures of different components or mixtures of thecomponents with farther polymers and/or different active ingredients.

Possible additional formulation excipients are

-   -   a) meltable sugar alcohols, sugars, fats and waxes (from 0 to        99%),    -   b) polymers, such as polyvinylpyrrolidone, cellulose        derivatives, polyvinylformamide (also partially or completely        hydrolyzed), copolymers, polyethylene glycols, starch and starch        derivatives, polyacrylates and polymethacrylates (Eudragit        types), polyvinyl alcohol, partially hydrolyzed polyvinyl        acetate and polyacrylamides (from 0 to 99%),    -   c) if required, assistants such as surfactants, disintegrants,        colorants, lubricants or plasticizers, dispersants, fillers or        salts and antifoams (from 0 to 99%) or other mixtures.

Other pharmaceutical excipients are added bases or acids for controllingthe solubility of an active ingredient.

There are no restrictions at all with regard to the active ingredientswhich can be formulated with the components described here. Exampleswhich may be mentioned are benzodiazepines, antihypertensive drugs,vitamins, cytostatic drugs, anesthetics, neuroleptics, antidepressants,antibiotics, antimycotic drugs, fungicides, chemotherapeutic drugs,urological drugs, platelet aggregation inhibitors, sulfonamides,spasmolytic drugs, hormones, immunoglobulins, sera, thyroidtherapeutics, psychotropic drugs, antiparkinson drugs and otherantihyperkinetic drugs, ophthalmic drugs, neuropathic preparations,calcium metabolism regulators, muscle relaxants, narcotics, lipiddepressants, hepatotherapeutic drugs, coronary drugs, cardiac drugs,immunotherapeutic drugs, regulator peptides and their inhibitors,hypnotics, sedatives, gynecological drugs, antigout drugs, fibrinolyticdrugs, enzyme preparations and transport proteins, enzyme inhibitors,emetics, compositions for promoting blood flow, diuretics, diagnosticdrugs, corticoids, cholinergic drugs, drugs for the treatment of biliaryducts, antihistamines, broncholytic drugs, beta receptor blockers,calcium antagonists, ACE inhibitors, arteriosclerotic drugs,antiphlogistic drugs, anticoagulants, antihypotensive drugs,antihypoglycemic drugs, antihypertensive drugs, antifibrinolytic drugs,antiepileptic drugs, antiemetics, antidotes, antidiabetic drugs,antiarrhythmic drugs, antianemic drugs, antiallergic drugs,anthelmintics, analgesics, analeptics, aldosterone antagonists andslimming preparations.

Pharmaceutical and other formulations can be obtained by processing thecomponents (A) and/or (B) with pharmaceutical or other activeingredients by conventional methods and with the use of known activeingredients.

In the preparation of the formulations, it is of course also possible toadd further excipients conventionally used in the preparation of solidoral dosage forms. These may be substances from among fillers andbinders (for example lactose, calcium phosphates, cellulose and itsderivatives, starch, polyvinylpyrrolidone, polyvinylformamide (alsopartially or completely hydrolyzed), polyvinyl alcohol, partiallyhydrolyzed polyvinyl acetate, polyacrylamides (from 0 to 99%), sugaralcohols, sugars, fats or waxes (from 0 to 99%)),

-   -   disintegrants (for example Kollidon C L, according to the claim        carboxymethyl starch or carboxymethylcellulose),    -   lubricants (for example magnesium stearate, calcium behenate,        stearic acid or PEG),    -   flow regulators (for example finely divided silica),    -   film formers (for example polyacrylates and polymethacrylates        (Eudragit types),    -   copolymers based on acrylate derivatives,        hydroxypropylmethylcellulose, hydroxypropylcellulose, cellulose        acetate, cellulose acetate phthalate and other coating materials        resistant to gastric fluid),    -   humectants (for example glycerol, propylene glycol, sorbitol,        mannitol or polyethylene glycols),    -   plasticizers, colorants, surfactants, salts and dispersants.

Use as Assistants for Plasticizing Concrete

Regarding this use, reference may be made to DE-A 196 53 524, whosecontent in this respect is hereby fully incorporated by reference in thecontext of the present application. Reference may be made in particularto the section of this patent application beginning on page 10, line 51to page 11, line 37.

The novel components (A) or (B) are extremely useful as additives forcement mixes, such as concrete or mortar. Cement is to be understood asmeaning, for example, Portland cement, high-alumina cement or mixedcement, for example pozzolanic cement, slag cement or other types.Portland cement is preferred. The copolymers are used in an amount offrom 0.01 to 10, preferably from 0.05 to 3, % by weight based on theweight of the cement.

The components (A) and (B) can be added in solid form, which isobtainable by drying, for example spray-drying, of polymer solutions ordispersions as obtained in the polymerization, to the ready-to-usepreparation of the mineral building material. It is also conceivable toformulate the copolymers with the mineral binder and to prepare theready-to-use preparation of the mineral building materials therefrom.Preferably, the copolymer is used in liquid, i.e. dissolved, emulsifiedor suspensed, form, for example in the form of the polymerizationsolution, in the preparation of the mineral building material.

For use in concrete and mortar, it may be advantageous to employpolymers which are converted into a water-soluble and hence active formonly in the presence of the alkaline concrete or mortar, for examplepolymers containing carboxylic acid or carboxylic anhydride structures.The slow release of the active polymer results in a longer-lastingactivity.

The novel components (A) and (B) can also be used in combination withthe known concrete plasticizers based on the sulfonate of anaphthalene/formaldehyde condensate, the sulfonate of amelamine/formaldehyde condensate, a phenolsulfonic acid/formaldehydecondensate and ligninsulfonates. They can also be used in combinationwith high molecular weight polyethylene oxides (molecular weight from100,000 to 8,000,000). Furthermore, they can be used together withcelluloses, for example alkyl- or hydroxyalkylcelluloses, starches orstarch derivatives. Additives such as air pore formers, expansioncompositions, water repellents, setting retardants, settingaccelerators, antifreezes, sealants, pigments, corrosion inhibitors,flowability additives, grouting aids, stabilizers and hollowmicrospheres may furthermore be admixed.

In principle, the novel components (A) and (B) can also be used togetherwith film-forming polymers. These are understood as meaning thosepolymers whose glass transition temperature (DSC midpoint temperature,ASTM D 3481–82) is ≦65° C., preferably ≦50° C., particularly preferably25° C., very particularly preferably ≦0° C. On the basis of therelationship between the glass transition temperature of homopolymersand the glass transition temperature of copolymers, postulated by Fox(T. G. Fox, Bull. Am. Phys. Soc. (Ser.II) 1 (1956), 123), those skilledin the art are able to select suitable polymers (glass transitiontemperatures for homopolymers are to be found, for example, in UllmannsEncyclopedia of Industrial Chemistry, Vol. A21, VCH, Weinheim 1992, page169, or in J. Brandrup, E. H. Immergul, Polymer Handbook, 3^(rd) Ed., J.Wiley, New York 1998).

Furthermore, it is often advantageous if the novel components (A) and(B) are used together with antifoams. This prevents too much air frombeing introduced into the concrete in the form of air pores during thepreparation of the ready-to-use building materials, which air poreswould reduce the strength of the set mineral building material. Suitableantifoams comprise in particular polyalkylene oxide-based antifoams,such as polyethylene oxide, polypropylene oxide, dialkyl ethers, such asdiethylene glycol heptyl ether, polyethylene oxide oleyl ether,polypropylene oxide dibutyl ether, polyethylene oxide 2-ethylhexyl etheror polypropylene oxide 2-ethylhexyl ether. Also suitable are theethoxylation products and the propoxylation products of alcohols of 10to 20 carbon atoms, ethoxylated/propoxylated (alkyl)phenol, such aspropoxylated phenol (degree of propoxylation from 2 to 40) andethoxylated (alkyl)phenol (degree of ethoxylation from 2 to 50). Thediesters of alkylene glycols or polyalkylene glycols, such as diethyleneglycol dioleate or ethylene glycol distearate, or aliphatic acid estersof alkylene oxide sorbitans, such as polyethylene oxide sorbitanmonolaurate or polyethylene oxide sorbitan trioleate, are also suitable.Other suitable antifoams are phosphoric esters, such as tributylphosphate or triisobutyl phosphate, phthalates, such as dibutylphthalates, to siloxanes, such as polydiniethylsiloxane and itsderivatives, as obtained, for example, by hydrosilylation with allylalkoxylates. Anionic antifoams, such as the sulfuric monoesters ofethoxylated (alkyl)phenols, for example the sodium salt of methylpolypropylene oxide sulfate and the sodium salt of n-dodecylphenolethoxylate sulfate, or phosphates of ethoxylated fatty alcohols, such aspolyethylene oxide stearyl phosphate, are furthermore suitable. Suchantifoams are usually used in amounts of from 0.05 to 10, preferablyfrom 0.5 to 5, % by weight, based on the polymers.

The antifoams can be combined with the polymer in various ways. If thepolymer is present, for example, in the form of an aqueous solution, theantifoam can be added in solid or dissolved form to the polymersolution. If the antifoam is insoluble in the aqueous polymer solution,emulsifiers or protective colloids may be added to stabilize it.

If the novel components (A) and (B) are present in the form of a solid,as obtained, for example, from spray-drying or fluidized-bedgranulation, the antifoam can be admixed in the form of a solid or, inthe case of the spray-drying process or spray granulation process, canbe compounded together with the polymer.

Use as Biodegradable Polymers, for Example as Materials for Implants,Surgical Suture Materials and Garbage Bags

Regarding this use of the components (A) and (B) described herein,reference may be made to EP-A 0 654 492, in particular to the sectionextending from page 7, line 53 to page 11, line 39.

The novel components (A) and (B), in particular when aliphaticpolyesters are involved, can be used, for example, as biodegradablepolymers for implants, surgical suture material and garbage bags.

For use as garbage bags, the components under discussion here are moldedby a generally customary blow molding method to give such articles. Ifconventional packaging materials, such as packaging containers forfoods, are to be produced, the novel components can also be prepared inthe form of foams, conventional methods being employed in turn here.

If the novel components have fiber-forming properties, as is the case,for example, with polyesters, they can be spun into fibers, which thenin turn can be used, for example, for surgical suture materials, owingto their biodegradability.

They are used in the form of individual fibers or in the form of fiberfabrics.

For fiber production, too, conventional methods are employed.

Use as Component in Water-Soluble Adhesives, for Example WallpaperAdhesives

In this use of the components (A) and (B), reference may be made to EP-A0 393 491 for further details. Thus, the present invention also relatesto the use of the components (A) and/or (B) as redispersion polymers infree-flowing fine-particle dry powders based on a water-soluble and/orwater-swellable combination of these components with nonionic celluloseethers, if necessary as a mixture with further assistants and/or withoutadhesive power.

The present invention also accordingly relates to free-flowingfine-particle dry powders based on a water-soluble and/orwater-swellable combination of nonionic cellulose ethers and driedredispersion polymers, if desired as a mixture with further assistantswith and/or without adhesive power. According to the invention, in thesefree-flowing fine-particle dry powders, the particle structure of the atleast predominant fraction of the particulate dry material has closedcores of the nonionic cellulose ethers which are surrounded by a shellof the redispersion polymer or firmly bonded thereto. In the respectiveindividual particle, in particular a majority of cores of nonioniccellulose ethers can be firmly enclosed by the polymer shell, it beingpossible for these individual cores based on the nonionic celluloseethers also to have different particle sizes. Nonionic cellulose ethersare understood by those skilled in the art as meaning alkyl, aralkyl andhydroxyalkyl ethers or cellulose. There are simple ethers having onlyone substituent and mixed ethers having two or more differentsubstituents in the cellulose chain. Thus, for example in the case ofmethylcellulose, the solubility and the flocculation point of thecellulose derivative can be influenced in a specific manner by anadditional, slight alkoxylation by reaction with ethylene oxide and/orpropylene oxide.

These free-flowing fine-particle dry powders are prepared by thoroughmixing of the nonionic cellulose ethers in powder form or in the form ofan aqueous powder suspension with the aqueous polymer dispersion, itbeing possible, if desired, also to mix in additional amounts of water.

Suitable nonionic cellulose ethers for the purposes of the invention areall compounds of this type which in their dissolution behaviour exhibitthe phenomenon of flocculation at elevated temperatures, preferably attemperatures or at least about 60° C., and are thus to be characterizedby the turbidity or flocculation point. If necessary. this property canbe rapidly and easily determined by a laboratory experiment.Alkylcelluloses are particularly suitable here. The most important classcomprises lower alkylcelluloses whose alkyl radicals have in particular1 to 3 carbon atoms. The member of this class which is widely used inpractice is methylcellulose. The degree of etherification of suchnonionic cellulose ethers may be, for example, in the range of fromabout 1.0 to 1.3 as the lower limit and up to 2.5 to 3.0 as the upperlimit, in particular in the range from 1.3 to 2.6. The cellulose ethers,preferably methylcellulose, may additionally be alkoxylated, for exampleethoxylated and/or propoxylated, and degrees of alkoxylation of fromabout 0.05 to 1.5 may be preferred here.

Suitable polymer compounds redispersible in water are the reactionproducts (A) and/or polymers (B) described herein. Both homopolymersand/or copolymers of the classes of substances selected in each case aresuitable here. Typical members of these polymer compounds are vinylesters of lower carboxylic acids, vinyl acetate and/or vinyl propionatebeing particularly important. In addition to the is homopolymers of thistype, copolymers, for example vinyl acetate/maleate copolymers orethylene/vinyl acetate copolymers, are used in practice. A furtherimportant class comprises corresponding (meth)acrylate homo- and/orcopolymers, an example of suitable copolymers being styrene acrylate.

These aqueous polymer dispersions comprising component (A) and/or (B)are now subjected to spray-drying not as such but rather—if desiredafter dilution with further amounts of water—after heating to atemperature level which corresponds at least to the turbidity orflocculation point of the nonionic cellulose ether or ethers to beincorporated. Temperatures which are slightly, for example from 10 to20° C., above the respective turbidity point can preferably be employed.

If such a slurry is kept permanently at, such a temperature level, it ispossible without problems to incorporate even large amounts of thenonionic alkylcellulose ethers as preformed dry powder into the liquidphase without thereby shifting the viscosity of the slurry into regionswhich would make the use of the spray technology impossible. Under theconditions according to the invention, there is instead a limitedincrease in the slurry viscosity, for example in the range whichotherwise also occurs with addition of inert additives, for example withthe addition of alpha-cellulose powder having a similar particledistribution or other conventional fillers.

The mixing ratios of nonionic cellulose ether to redispersion polymer,calculated in each case as a solid, may be varied within a wide range.In particular, corresponding mixing ratios of from about 5:95 to 95:5are suitable. Preferred mixing ratios of these two main components areroughly in the range from 60:40 to 40:60, good products being obtainedin the region of about identical ratios or with only a slight excess,based on weight, of the nonionic cellulose ethers.

On spraying such a slurry, a free-flowing fine-particle dry product isobtained, which virtually exclusively comprises polymer-coated nonionicalkylcellulose cores of a relatively uniform composition and particlestructure. The mean particle size of the novel products, based on theinitial grading curve of the cellulose ethers used, for example in theform of methylcellulose used, is substantially above the mean particlesize applicable to commercial redispersion powders. It may be preferableto bring the novel free-flowing powders to mean particle diameters offrom about 50 to 500 μm, preferably from about 100 to 300 μm.

Furthermore, the particles described above may undergo at least partialagglomeration, which results in agglomerates which consist of at leasttwo, formerly independent particles which may be joined to one anotherwith different adhesive strengths.

In contrast to physical mixtures, the spray-dried products obtainedaccording to the invention do not give rise to any significant amountsof dust, which is to be regarded as a considerable advantage in theirprocessing.

According to a further feature of the invention, it is possible toincorporate additional assistants with and/or without adhesiveproperties into the novel free-flowing fine-particle powders.

Examples of such assistants are wetting agents and preservatives,consistency-imparting substances and additional components havingadhesive power, such as natural starch, swellable starch, starch ethers,dextrins, ionic cellulose ethers and/or other aqueous polymerformulations.

These assistants present in addition to the main components preferablyaccount for a constantly minor amount compared with the main componentscomprising nonionic cellulose ether and redispersion polymer.

The spray-drying is effected in a manner known per se, usually in spraytowers, and the slurry to be dried can be sprayed in with the aid ofatomizing disks or airless or binary nozzles.

The field of use of the novel multicomponent powders covers the entirearea for the use of such mixtures of substances. Examples are the use aswall covering adhesives, in particular wallpaper adhesives, and the useas an improving additive to coating materials, such as paints andvarnishes, and to cement-based systems. These powders are particularlysuitable as additives in filling and leveling compounds, tile adhesivesand plaster-based filling compounds. Products spray-dried according tothe invention constitute a raw material which permits access to hithertounachieved application benefits in the adhesives and building chemicalssector, within wide ranges.

For further details regarding the type of the further components and thepreparation of the dry powder described above, reference may be made toEP-A 0 393 491.

Use as Adhesive for Floor Coverings

The present invention furthermore relates to the use of components (A)and (B) in the form of aqueous adhesive compositions, in particular asadhesives for floor coverings. For this purpose, the components (A)and/or (B) are mixed with polyurethane latices in a manner known per se,if required an inert filler, a plasticizer and a crosslinking agent alsobeing part of the composition. The amount of the components (A) and/or(B) varies within a range from 1 to 20% by weight. Further detailsregarding this application are given in U.S. Pat. No. 5,455,293, whosedisclosure in this context is hereby fully incorporated in the contextof the present application.

Use as Thickener of Aqueous or Predominantly Aqueous Systems

The novel components (A) and (B) are suitable for thickening aqueous orpredominantly aqueous systems, such as surface coatings, print pastesand pigment pastes, filler and pigment dispersions, textiles, leatherand paper assistants, formulations for mineral oil production,formulations of detergents, adhesives, waxes for polishes, formulationsfor pharmaceutical and veterinary purposes, crop protectionformulations, cosmetic articles, etc. Water itself can also be thickenedwith the novel components (A) and (B) in order subsequently, ifrequired, to add further additives to said water or to add said wateritself to aqueous formulations. The novel thickeners can be used inmixtures with other thickeners, for example those based onpolyacrylates, cellulose derivatives or inorganic thickeners.

Examples of aqueous systems which can be thickened according to theinvention are aqueous polyacrylate dispersions, aqueous dispersions ofcopolymers of olefinically unsaturated monomers, aqueous polyvinylacetate dispersions, aqueous polyurethane dispersions, aqueous polyesterdispersions and in particular ready-to-use formulations of the typediscussed above and based on such dispersions.

The novel components (A) and (B) can of course be used as such,preferably in the form of granules or, if required, powders. However,liquid formulations which, in addition to the novel polyurethanes,contain water, solvents, such as butyldiglycol, isopropanol,methoxypropyl acetate, ethylene glycol and/or propylene glycol, nonionicemulsifiers, surfactants and/or, if required, further additives arepreferably used since this substantially facilitates the incorporationof the novel thickeners into aqueous or predominantly aqueous systems.

The ready-to-use formulations of the novel components (A) and (B) areparticularly preferably aqueous solutions or dispersions having a solidscontent of from 10 to 80, preferably from 30 to 60, particularlypreferably from 40 to 50, % by weight.

The amount of the novel components (A) and (B) which are added to theaqueous or predominantly aqueous systems for achieving the desiredthickening depends on the respective intended use and can be determinedby those skilled in the art in a few experiments. As a rule, from 0.05to 10, preferably from 0.1 to 4, particularly preferably from 0.1 to 1,% by weight of the novel components (A) and (B) are used, thesepercentages being based on the solids content of the components (A) and(B) on the one hand and on the solids content of the aqueous system tobe thickened, on the other hand.

Use as Component in Pressure-Sensitive Adhesive Materials

The components (A) and (B) described herein can also be used ascomponents in pressure-sensitive adhesive materials. Such components (A)and/or (B) based on block copolymers containing polymer blocks formedfrom vinylaromatics (A blocks), preferably styrene, and those formed bypolymerization of 1,3-dienes (D blocks), preferably butadiene andisoprene, are preferably employed.

According to the invention, both homopolymer and copolymer blocks can beused. The resulting block copolymers may contain identical or differentD blocks, some or all of which can be completely hydrogenated or whichcan be selectively hydrogenated. Block copolymers may have a linearA-D-A structure. Block copolymers having a radial structure and star andlinear multiblock copolymers may also be used. A-D two-block copolymersmay be present as further components. Block copolymers may be modified,for example functionalized by reaction with maleic anhydride. Accordingto the invention, block copolymers of vinylaromatics and isobutylene canalso be used. All of the abovementioned polymers can be used alone or inmixture with one another. Typical concentrations in which the styreneblock copolymers are used are from 15 to 75, preferably from 30 to 60,particularly preferably from 35 to 55, % by weight.

Suitable tackifiers include: colophony and its derivatives, aliphatic,aromatically modified aliphatic, aromatic and phenol-modified adhesiveresins, to mention but a few. The concentrations in which the resins areused are typically from 15 to 75, preferably from 30 to 65, particularlypreferably from 35 to 60, % by weight. Where colophony and itsderivatives are used, esters of partially and completely hydrogenatedcolophony are preferably employed.

Homopolymers and copolymers of vinylaromatics, for example styrene orα-methylstyrene, polyphenylene oxides and also phenylene oxide-modifiedresins may be used as resins compatible with the terminal blocks,chiefly resins compatible with the vinylaromatic blocks.

Further optimum components of the mixture comprise plasticizer oils andliquid resins (concentration of use from 0 to not more than about 35% byweight), fillers (reinforcing and nonreinforcing), for example silica,in particular synthetic silica, glass (milled or in the form of beads),aluminas, zinc oxides, calcium carbonates, titanium dioxide, carbonblacks, to mention but a few, and antiaging compositions (primary andsecondary antioxidants, light stabilizers, antiozonants, metaldeactivators, etc.). Components of the mixture also comprise polymerswhich in particular affect the ozone resistance of the block copolymers,for example polyvinyl acetates and ethylene/vinyl acetate copolymers.

Further polymers which may be used are natural and synthetic polymers,for example natural rubber, synthetic polyisoprenes, polybutadienes,polychloroprenes. SBR, Kraton Liquid (Shell Chemicals), low molecularweight styrene/diene block copolymers, for example Kraton LVSI 101,polyisobutylene, etc., which may replace up to about 50% by weight ofthe vinylaromatic-containing block copolymers.

Novel pressure-sensitive adhesive materials may have been chemicallycrosslinked, in particular radiation-crosslinked (for example by UVirradiation, γ-irradiation or irradiation by means of fast electrons).

Novel adhesive materials are optionally those whose tack is producedonly as a result of thermal activation.

Suitable pressure-sensitive adhesive materials in addition to thosedescribed above and based on vinylaromatic-containing block copolymersare all those which have tensile strength and cohesion sufficient forthe release process. Corresponding pressure-sensitive adhesive materialscan be used alone or in combination with those based onvinylaromatic-containing block copolymers. For example, tacky acrylatecopolymers copolymerized with macromonomers are suitable according tothe invention, the macromonomers having a glass transition temperatureof >+40° C. The high tensile strength of corresponding copolymers isprobably achieved by the association of the macromonomers. Suitablemacromonomers are, for example, methacryloyl-terminated polymethylmethacrylates,

The pressure-sensitive adhesive materials described above can be usedfor self-adhesive tapes for tamper-proof applications, the fixing ofposters, pictures, calendars, postcards, information signs,self-adhesive hooks and labels, for example price labels, and for theadhesive bonding of foam.

Regarding this use, reference may be made to DE-A 196 49 728, whoserelevant content on pages 3 and 4 is hereby fully incorporated byreference in the context of the present application.

Use as Solid or Liquid Adhesive

According to the present inventor, the components (A) and (B) can alsobe used in solid adhesives in order to impart to them the adhesion whichthey produce. Particularly used components (A) and (B) are those whichmay be selected from the group consisting of polyvinyl acetatehomopolymers, polyvinyl acetate copolymers, partially or completelyhydrolyzed polyvinyl alcohol, polyvinyl butyral, polyvinylpyrrolidone,polyacrylic acid salts, polymethacrylic acid salts, polyacrylate,polymethacrylate, various gums, polysaccharides and rubber. Thecomponents (A) and/or (B) may be a mixture of more than one of thesechemicals. Preferably, the components (A) and/or (B) are a mixture ofpolyvinyl alcohol and polyvinylpyrrolidone. It has been found that atleast about 15%, preferably at least 20%, of the components (A) and/or(B) in the solid adhesive result in good adhesion by the solid adhesive.Too large an amount of the components (A) and/or (B) cannot be dissolvedin water. The components (A) and/or (B) are therefore preferably limitedto from about 15 to 42%, better still from about 20 to 36%, in the solidadhesive.

Benzylidenesorbitol is present in this solid adhesive in order to serveas a gelatinizing composition or gel former. Chemicals which may be usedas benzylidenesorbitol are those which are used as a benzylidenesorbitolin the references. Among these chemicals, dibenzylidene (penta- orhexahydro-)saccharide is preferred, dibenzylidenesorbitol beingparticularly preferred. At least about 0.3%, better still at least 0.8%,of benzylidenesorbitol should be present in the solid adhesive in orderto ensure appropriate strength properties of a stick-like productproduced from this solid adhesive. Too much benzylidenesorbitol cannotbe dissolved in organic solvents. The benzylidenesorbitol in the solidadhesive is therefore preferably limited to from about 0.3 to 6%, betterstill from about 0.8 to 4%.

At least about 25%, better still at least about 28%, of water is presentin the solid adhesive in order to facilitate the dissolution of thebenzylidenesorbitol. Too much water in the solid adhesive presentsdissolution of the benzylidenesorbitol and adversely affects theadhesion of the solid adhesive. Accordingly, the amount of water islimited to from about 25 to 60%, preferably from about 28 to 57%, in thesolid adhesive.

Since this solid adhesive contains a large amount of water, it ispossible for various microorganisms to multiply in the solid adhesiveduring prolonged storage and release. The growth of variousmicroorganisms adversely affects the properties of the solid adhesive.To prevent the growth of various microorganisms in the solid adhesive,the latter contains at least 0.001%, preferably 0.003%, better still atleast 0.005%, of a preservative, for example an isothiazolinepreservative. Too high a content of isothiazoline preservativesadversely affects the physical properties of the solid adhesive andresults in higher costs of the solid adhesive. Accordingly, theisothiazoline preservatives are limited to from about 0.001 to 0.5%,preferably from about 0.003 to 0.1%, better still from about 0.005 to0.05%, in the solid adhesive. The isothiazoline preservatives can beselected from the group consisting of 1,2-benzisothiazolin-3-one,methylisothiazoline, octylisothiazoline and isothiazolinone.Isothiazoline preservatives may be a mixture of more than one of thesechemicals. Among these chemicals, 1,2-benzisothiazolin-3-one ispreferred.

At least about 12% and preferably at least 13% of organic solvent ispresent in the solid adhesive in order to facilitate the dissolution ofbenzylidenesorbitol. Too high a content of solvent adversely affects theadhesive and strength properties of a stick-like product produced fromsolid adhesive. Accordingly, the organic solvents are preferably limitedto from about 12 to 50%, better still from about 13 to 43%. Suitableorganic solvents are water-miscible organic solvents, preferably polarorganic solvents. The organic solvents can be selected in particularfrom the group consisting of various alcohols, glycol alkyl ethers,alkyl ethers and pyrrolidone derivatives. In particular, the organicsolvent can be selected from the group consisting of3-methoxy-3-methyl-1-butanol, N-methyl-2-pyrrolidone, 2-butoxyethanol,isopropyl alcohol, 1-ethoxy-2-propanol, 1-methoxy-2-propanol and2-ethoxyethanol. The organic solvent may be a mixture of more than oneof these chemicals. Among these, glycol (of 2 to 6 carbon atoms) alkyl(of 1 to 3 carbon atoms) monoether is particularly preferred.

Further chemicals may be present in this solid adhesive. For example,from 0.1 to 1%, preferably from about 0.3 to 0.7%, of antirustcompositions may be present in the solid adhesive on shaping of saidadhesive and when said adhesive is shaped into a stick-like product, inorder to prevent the formation of rust on metallic parts. Preferably,benzotriazole corrosion inhibitor is present in the solid adhesive. Inaddition, fragrances and/or pigments may be present in the solidadhesive.

Solid adhesives in the context of the present text are all types ofadhesives which are present in the solid state at ambient temperature,for example at room temperature. These include in particular hotmeltadhesives, hotmelt pressure-sensitive adhesives and pressure-sensitiveadhesives. Said adhesives can also be applied, for example, to substratematerials, for example to tape-like substrate materials, as used in theproduction of adhesive tapes.

Regarding further details, reference may be made to DE-A 197 55 683.

Use for Producing Self-Cleaning Surfaces of Articles (Lotus Effect)

The novel components (A) and (B), in particular the novel blockcopolymers, are extremely useful for producing self-cleaning surfaces ofarticles, as described, for example, in WO 96/04123, the relevantcontent of which is hereby fully incorporated by reference in thecontext of the present application. Particularly advantageous blockcopolymers are those which, owing to the incompatibility of theirrespective blocks form self-cleaning (i.e. hydrophobic andcorrespondingly structured) surfaces by self-organization afterapplication.

Use as Stain Inhibitors in Solid and Liquid Formulations

The novel components (A) and (B) can also be used as stain inhibitors insolid and liquid formulations. In this application, they are used inparticular in detergents.

In this respect, reference may be made to the publication in ResearchDisclosure of August 1998, page 1047 et seq., the relevant content ofwhich is hereby fully incorporated by reference in the context of thepresent application.

1. Coating materials comprising a reaction product (A) which is preparedby means of a process comprising the following stage (i): (i) Reaction,under free radical conditions, of a reaction mixture comprising at leastone monomer (a), capable of free radical reaction, in the presence of atleast one radical of the formula (III)

 where R₁ to R₃, in each case independently of one another, arehydrogen, methyl or a radical-stabilizing and/or bulky group selectedfrom the group consisting of unsubstituted and substituted, linear andbranched alkyl groups having two or more carbon atoms, cycloalkyl,alcohol, ether, polyether, amine and aralkyl radicals, substituted andunsubstituted aromatic, heterocyclic and olefinic hydrocarbons, halogenatoms, substituted and unsubstituted, linear and branched alkenyl andalkynyl groups, —C(O)R₅, —C(O)OR₅, —CR₅R₆—O—R₇, —O—C(O)R₅, —CN, —O—CN,—S—CN, —O—C═NR₅, —S—C═NR₅, —O—CR₅R₆—CR₇R₈NR₉R₁₀, —N═C═O, —C═NR₅,—CR₅R₆-Hal, —C(S)R₅, —CR₅R₆—P(O)R₇R₈, —CR₅R₆—PR₇R₈, —CR₅R₆—NR₇R₈,—CR₅R₆(OR₇)(OR₈), —CR₅R₆(OR₇)(NR₈), —CR₅R₆(NR₇)(NR₈), anhydride, acetaland ketal groups, —SO₂R₅, amidine groups, —NR₅C(S)NR₆, —NR₅C(S)—OR₆,—N═C═S, —NO₂, —C═N—OH, —N(R₅)═NR₆, —PR₅R₆R₇, —OSiR₅R₆R₇ and —SiR₅R₆R₇,where R₅ to R₁₀, independently of one another in each case, are definedin the same way as R₁ to R₄, or two of the radicals R₁ to R₄ form a C₄-to C₇-ring which in turn may be substituted or unsubstituted and,optionally, contain one or more heteroatom, with the proviso that atleast two of the radicals R₁ to R₃ are a radical-stabilizing and/orbulky group as defined above, or a polymer (B) which is prepared by aprocess comprising the stage (ii): (ii) Reaction of the reaction product(A) obtained in stage (i), under free radical conditions, in thepresence of at least one monomer (b) capable of free radicalhoinopolymerization or copolymerization, and suitable additives (C)selected from the group consisting of crosslinking agents, crosslinkingcatalysts, initiators, pigments, dyes, fillers, reinforcing fillers,rheology assistants, wetting agents, dispersants, antifoams, adhesionpromoters, additives for improving substrate wetting, additives forimproving surface smoothness, dulling agents, leveling agents,film-forming assistants, drying agents, antiskinning agents, lightstabilizers, corrosion inhibitors, biocides, flameproofing agents,polymerization inhibitors, photoinhibitors and plasticizers.
 2. Coatingmaterials as claimed in claim 1, wherein the radical of the formula(III) is derived from at least one compound of the formula (I)

where R₁ to R₄, in each case independently of one another, are hydrogen,methyl or a radical-stabilizing and/or bulky group selected from thegroup consisting of unsubstituted and substituted, linear and branchedalkyl group having two or more carbon atoms, cycloalkyl, alcohol, ether,polyether, amine and aralkyl radicals, substituted and unsubstitutedaromatic, heterocyclic and olefinic hydrocarbons, halogen atoms,substituted and unsubstituted, linear and branched alkenyl and alkynylgroups, —C(O)R₅, —C(O)OR₅, —CR₅R₆—O—R₇, —O—C(O)R₅, —CN, —O—CN, —S—CN,—O—C═NR₅, —S—C═NR₅, —O—CR₅R₆—CR₇R₈NR₉R₁₀, —N═C═O, —C═NR₅, —CR₅R₆-Hal,—C(S)R₅, —CR₅R₆—P(O)R₇R₈, —CR₅R₆—PR₇R₈, —CR₅R₆—NR₇R₈, —CR₅R₆(OR₇)(OR₈),—CR₅R₆(OR₇)(NR₈), —CR₅R₆(NR₇)(NR₈), anhydride, acetal and ketal groups,—SO₂R₅, amidine groups, —NR₅C(S)NR₆, —NR₅C(S)—OR₆, —N═C═S, —NO₂,—C═N—OH, —N(R₅)═NR₆, —PR₅R₆R₇, —OSiR₅R₆R₇ and —SiR₅R₆R₇, where R₅ toR₁₀, independently of one another in each case, are defined in the sameway as R₁ to R₅, or two of the radicals R₁ to R₄ form a C₄- to C₇-ringwhich in turn may be substituted or unsubstituted and may contain one ormore heteroatoms, with the proviso that at least two of the radicals R₁to R₄ are a radical-stabilizing and/or bulky group, as defined above, orthe compounds are diphenylethylene, dinaphthylethylene,4,4′-vinylidenebis(N,N′-dimethylaniline)4,4′-vinylidenebis(aminobenzene) or cis- and trans-stilbene.
 3. Coatingmaterials as claimed in claim 1, wherein the radical of the formula(III) is derived from at least one compound of the formula (II):

where R₁ to R₄ and R₁₁ and R₁₂, in each case independently of oneanother, are hydrogen, methyl or a radical-stabilizing and/or bulkygroup selected from the group consisting of unsubstituted andsubstituted, linear and branched alkyl groups having two or more carbonatoms, cycloalkyl, alcohol, ether, polyether, amine and aralkylradicals, substituted and unsubstituted aromatic, heterocyclic andolefinic hydrocarbons, halogen atoms, substituted and unsubstituted,linear and branched alkenyl and alkynyl group, —C(O)R₅, —C(O)OR₅,—CR₅R₆—O—R₇, —O—C(O)R₅, —CN, —O—CN, —S—CN, —O—C═NR₅, —S—C═NR₅,—O—CR₅R₆—CR₇R₈NR₉R₁₀, —N═C═O, —C═NR₅, —CR₅R₆-Hal, —C(S)R₅,—CR₅R₆—P(O)R₇R₈, —CR₅R₆—PR₇R₈, —CR₅R₆—NR₇R₈, —CR₅R₆(OR₇)(OR₈),—CR₅R₆(OR₇)(NR₈), —CR₅R₆(NR₇)(NR₈), anhydride, acetal and ketal groups,—SO₂R₅, amidine groups, —NR₅C(S)NR₆, —NR₅C(S)—OR₆, —N═C═S, —NO₂,—C═N—OH, —N(R₅)═NR₆, —PR₅R₆R₇, —OSiR₅R₆R₇ and —SiR₅R₆R₇, where R₅ toR₁₀, independently of one another in each case, are defined in the sameway as R₁ to R₄, or two of the radicals R₁ to R₄ form a C₄- to C₇-ringwhich in turn may be substituted or unsubstituted and, optionally,contain one or more heteroatoms, with the proviso that at least two ofthe radicals R₁ to R₄ are a radical-stabilizing and/or bulky group, asdefined above.
 4. Coating materials as claimed in claim 1, the radicalof the formula (III) comprising the following combinations asradical-stabilizing and/or bulky groups: at least one substituted orunsubstituted phenyl and —C(O)R₅; at least one substituted orunsubstituted phenyl and —CN; at least one substituted or unsubstitutedphenyl and —C(O)OR₅; independently of one another, at least twosubstituted or unsubstituted phenyl groups; independently of oneanother, at least two —C(O)R₅; and independently of one another, atleast two —CN.
 5. Coating materials as claimed in claim 1, the radical(III) being derived from the following compounds of the formula (I) or(II) or mixtures of two or more thereof:1,1,4,4-tetraphenyl-1,3-butadiene 1,4-bis(2-methylstyryl)benzene1,2,3,4,5-pentaphenyl-1,3-cyclopentadiene1,2,3,4-tetraphenyl-1,3-cyclopentadiene acenaphthylene cis- andtrans-alpha-methylstilbene cis- and trans-4,4′-diphenylstilbene,diphenylethylene, dinaphthylethylene,4,4′-vinylidenebis(N,N′-dimethylaniline),4,4′-vinylidenebis(aminobenzene), cis- and trans-stilbene, trans-trans-and trans-cis- and cis-cis-1,4-diphenyl-1,3-butadienealpha,omega-tetraphenylpolyethyne diphenylfulvene triphenylethenetetraphenylethene 1-cyano-1-phenylethylene;1-alkoxycarbonyl-1-phenylethylene; 1,1-dialkoxycarbonyl-2-ethylethylene;1,1-dialkoxycarbonyl-2-phenylethylene,1,1-dialkoxycarbonyl-2,2-dimethylethylene;1,1-dialkoxycarbonylmethylethylene; 9-methylenexanthene;9-methylenethioxanthene, 9-methylene-10-H-acridine, diphenylethylene,dinaphthylethylene, 4,4′-vinylidenebis(N,N′-dimethylaniline),4,4-vinylidenebis(aminobenzene), cis- and trans-stilbene,1,2-bis(trimethylsilyloxy)tetraphenylethane (TPSE),diethyl-2,3-dicyano-2,3-di(p-tolyl)succinate, hexaphenylethane,compounds of the structure (Ph₂CR₁—CR₁(Ph)₂, where Ph is substituted orunsubstituted phenyl and R₁ is selected from the group consisting of:hydrogen, ethyl, —C₂H₄—, —OC₆H₅, OSi(CH₃)₃, —OH, —OC(O)CH₃, —OCH₃, —CH₃,—CO₂C₂H₅, —CN; —OC(O)CH═CH₂, 1,1,2,2-tetraphenyl-1,2-diphenoxyethane(TPPA); 1,1,2,2-tetraphenyl-1,2-bis(trimethylsilyloxy)ethane (TPSA) and1,2,2,2-tetraphenyl-1,2-dicyanoethane (TPCA);1,2-diphenyl-1,2-dicyano-1,2-dimethylethane.
 6. Coating materials asclaimed in claim 1, which are prepared in the presence of a lowmolecular weight base selected the group consisting of NaOH, KOH,ammonia, diethanolamine, triethanolamine, mono-, di- and triethylamine,dimethylethanolamine and a mixture of two or more thereof.
 7. Resinmaterials comprising a reaction product (A) which is prepared by meansof a process comprising the following stage (i): (i) Reaction, underfree radical conditions, of a reaction mixture comprising at least onemonomer (a), capable of free radical reaction, in the presence of atleast one radical of the formula (III)

 where R₁ to R₃, in each case independently of one another, arehydrogen, methyl or a radical-stabilizing and/or bulky group selectedfrom the group consisting of unsubstituted and substituted, linear andbranched alkyl groups having two or more carbon atoms, cycloalkyl,alcohol, ether, polyether, amine and aralkyl radicals, substituted andunsubstituted aromatic, heterocyclic and olefinic hydrocarbons, halogenatoms, a substituted and unsubstituted, linear and branched alkenyl andalkynyl groups, —C(O)R₅, —C(O)OR₅, —CR₅R₆—O—R₇, —O—C(O)R₅, —CN, —O—CN,—S—CN, —O—C═NR₅, —S—C═NR₅, —O—CR₅R₆—CR₇R₈NR₉R₁₀, —N═C═O, —C═NR₅,—CR₅R₆-Hal, —C(S)R₅, —CR₅R₆—P(O)R₇R₈, —CR₅R₆—PR₇R₈, —CR₅R₆—NR₇R₈,—CR₅R₆(OR₇)(OR₈), —CR₅R₆(OR₇)(NR₈), —CR₅R₆(NR₇)(NR₈), anhydride, acetaland ketal groups, —SO₂R₅, amidine groups, —NR₅C(S)NR₆, —NR₅C(S)—OR₆,—N═C═S, —NO₂, —C═N—OH, —N(R₅)═NR₆, —PR₅R₆R₇, —OSiR₅R₆R₇ and —SiR₅R₆R₇,where R₅ to R₁₀, independently of one another in each case, are definedin the same way as R₁ to R₄, or two of the radicals R₁ to R₄ form a C₄-to C₇-ring which in turn may be substituted or unsubstituted and,optionally, contain one or more heteroatom, with the proviso that atleast two of the radicals R₁ to R₃ are a radical-stabilizing and/orbulky group as defined above, or a polymer (B) which is prepared by aprocess comprising the stage (ii): (ii) Reaction of the reaction product(A) obtained in stage (i), under free radical conditions, in thepresence of at least one monomer (b) capable of free radicalhomopolymerization or copolymerization, and additives selected from thegroup consisting of lubricants, antistatic agents, antioxidants, heatstabilizers, ultraviolet absorbers, pigments, dyes, nucleating agents,rubbers, fillers, dulling agents, brightening compositions,flameproofing agents, blowing agents, mold release agents and mineraloil.
 8. Resin materials as claimed in claim 7, wherein the radical ofthe formula (III) is derived from at least one compound of the formula(I):

where R₁ to R₄ and R₁₁ and R₁₂, in each case independently of oneanother, are hydrogen, methyl or a radical-stabilizing and/or bulkygroup selected from the group consisting of unsubstituted andsubstituted, linear and branched alkyl groups having two or more carbonatoms, cycloalkyl, alcohol, ether, polyether, amine and aralkylradicals, substituted and unsubstituted aromatic, heterocyclic andolefinic hydrocarbons, halogen atoms, substituted and unsubstituted,linear and branched alkenyl and alkynyl groups, —C(O)R₅, —C(O)OR₅,—CR₅R₆—O—R₇, —O—C(O)R₅, —CN, —O—CN, —S—CN, —O—C═NR₅, —S—C═NR₅,—O—CR₅R₆—CR₇R₈NR₉R₁₀, —N═C═O, —C═NR₅, —CR₅R₆-Hal, —C(S)R₅,—CR₅R₆—P(O)R₇R₈, —CR₅R₆—PR₇R₈, —CR₅R₆—NR₇R₈, —CR₅R₆(OR₇)(OR₈),—CR₅R₆(OR₇)(NR₈), —CR₅R₆(NR₇)(NR₈), anhydride, acetal and ketal groups,—SO₂R₅, amidine groups, —NR₅C(S)NR₆, —NR₅C(S)—OR₆, —N═C═S, —NO₂,—C═N—OH, —N(R₅)═NR₆, —PR₅R₆R₇, —OSiR₅R₆R₇ and —SiR₅R₆R₇, where R₅ toR₁₀, independently of one another in each case, are defined in the sameway as R₁ to R₄, or two of the radicals R₁ to R₄ form a C₄- to C₇-ringwhich in turn may be substituted or unsubstituted and, optionally,contain one or more heteroatoms, with the proviso that at least two ofthe radicals R₁ to R₄ are a radical-stabilizing and/or bulky group, asdefined above, or the compounds are diphenylethylene,dinaphthylethylene, 4,4′-vinylidenebis(N,N′-dimethylaniline),4,4′-vinylidenebis(aminobenzene) or cis- and trans-stilbene.
 9. Theresin material as claimed in claim 7, wherein the radical of the formula(III) is derived from at least one compound of the formula (II):

where R₁ to R₄ and R₁₁ and R₁₂, in each case independently of oneanother, are hydrogen, methyl or a radical-stabilizing and/or bulkygroup selected from unsubstituted and substituted, linear and branchedalkyl groups two or more carbon atoms, cycloalkyl, alcohol, ether,polyether, and amine aralkyl radicals, substituted and unsubstitutedaromatic, heterocyclic and olefinic hydrocarbons, halogen atoms,substituted and unsubstituted, linear and branched alkenyl and alkynylgroups, —C(O)R₅, —C(O)OR₅, —CR₅R₆—O—R₇, —O—C(O)R₅, —CN, —O—CN, —S—CN,—O—C═NR₅, —S—C═NR₅, —O—CR₅R₆—CR₇R₈NR₉R₁₀, —N═C═O, —C═NR₅, —CR₅R₆-Hal,—C(S)R₅, —CR₅R₆—P(O)R₇R₈, —CR₅R₆—PR₇R₈, —CR₅R₆—NR₇R₈, —CR₅R₆(OR₇)(OR₈),—CR₅R₆(OR₇)(NR₈), —CR₅R₆(NR₇)(NR₈), anhydride, acetal and ketal groups,—SO₂R₅, amidine groups, —NR₅C(S)NR₆, —NR₅C(S)—OR₆, —N═C═S, —NO₂,—C═N—OH, —N(R₅)═NR₆, —PR₅R₆R₇, —OSiR₅R₆R₇ and —SiR₅R₆R₇, where R₅ toR₁₀, independently of one another in each case, are defined in the sameway as R₁ to R₄, or two of the radicals R₁ to R₄ form a C₄- to C₇-ringwhich in turn may be substituted or unsubstituted and, optionally,contain one or more heteroatoms, with the proviso that at least two ofthe radicals R₁ to R₄ are a radical-stabilizing and/or bulky group, asdefined above.
 10. The resin material as claimed in claim 7, the radicalof the formula (III) comprising the following combinations asradical-stabilizing and/or bulky groups: at least one substituted orunsubstituted phenyl and —C(O)R₅; at least one substituted orunsubstituted phenyl and —CN; at least one substituted or unsubstitutedphenyl and —C(O)OR₅; independently of one another, at least twosubstituted or unsubstituted phenyl groups; independently of oneanother, at least two —C(O)R₅; and independently of one another, atleast two —CN.
 11. The resin material as claimed in claim 7, the radical(III) being derived from the following compounds of the formula (I) or(II) or mixtures of two or more thereof:1,1,4,4-tetraphenyl-1,3-butadiene 1,4-bis(2-methylstyryl)benzene1,2,3,4,5-pentaphenyl-1,3-cyclopentadiene1,2,3,4-tetraphenyl-1,3-cyclopentadiene acenaphthylene cis- andtrans-alpha-methylstilbene cis- and trans-4,4′-diphenylstilbene,diphenylethylene, dinaphthylethylene,4,4′-vinylidenebis(N,N′-dimethylaniline),4,4′-vinylidenebis(aminobenzene), cis- and trans-stilbene, trans-trans-and trans-cis- and cis-cis-1,4-diphenyl-1,3-butadienealpha,omega-tetraphenylpolyethyne diphenylfulvene triphenylethenetetraphenylethene 1-cyano-1-phenylethylene;1-alkoxycarbonyl-1-phenylethylene; 1,1-dialkoxycarbonyl-2-ethylethylene;1,1-dialkoxycarbonyl-2-phenylethylene,1,1-dialkoxycarbonyl-2,2-dimethylethylene;1,1-dialkoxycarbonylmethylethylene; 9-methylenexanthene;9-methylenethioxanthene, 9-methylene-10-H-acridine, diphenylethylene,dinaphthylethylene, 4,4′-vinylidenebis(N,N′-dimethylaniline),4,4′-vinylidenebis(aminobenzene), cis- and trans-stilbene,1,2-bis(trimethylsilyloxy)tetraphenylethane (TPSE),diethyl-2,3-dicyano-2,3-di(p-tolyl)succinate, hexaphenylethane,compounds of the structure (Ph₂CR₁—CR₁(Ph)₂, where Ph is substituted orunsubstituted phenyl and R₁ is selected from the group consisting of:hydrogen, ethyl, —C₂H₄—, —OC₆H₅, OSi(CH₃)₃, —OH, —OC(O)CH₃, —OCH₃, —CH₃,—CO₂C₂H₅, —CN; —OC(O)CH═CH₂, 1,1,2,2-tetraphenyl-1,2-diphenoxyethane(TPPA); 1,1,2,2-tetraphenyl-1,2-bis(trimethylsilyloxy)ethane (TPSA) and1,2,2,2-tetraphenyl-1,2-dicyanoethane (TPCA);1,2-diphenyl-1,2-dicyano-1,2-dimethylethane.
 12. The resin material asclaimed in claim 7, which is prepared in the presence low molecularweight base selected from the group consisting of NaOH, KOH, ammonia,diethanolamine, triethanolamine, mono-, di- or triethylamine,dimethylethanolamine or a mixture of two or more thereof.
 13. Aqueousdispersion containing a reaction product (A) which is prepared by meansof a process comprising the following stage (i): (i) Reaction, underfree radical conditions, of a reaction mixture comprising at least onemonomer (a), capable of free radical reaction, in the presence of atleast one radical of the formula (III)

 where R₁ to R₃, in each case independently of one another, arehydrogen, methyl or a radical-stabilizing and/or bulky group selectedfrom the group consisting of unsubstituted and substituted, linear andbranched alkyl groups having two or more carbon atoms, cycloalkyl,alcohol, ether, polyether, amine and aralkyl radicals, substituted andunsubstituted aromatic, heterocyclic and olefinic hydrocarbons, ahalogen atoms, substituted and unsubstituted, linear and branchedalkenyl and alkynyl groups, —C(O)R₅, —C(O)OR₅, —CR₅R₆—O—R₇, —O—C(O)R₅,—CN, —O—CN, —S—CN, —O—C═NR₅, —S—C═NR₅, —O—CR₅R₆—CR₇R₈NR₉R₁₀, —N═C═O,—C═NR₅, —CR₅R₆-Hal, —C(S)R₅, —CR₅R₆—P(O)R₇R₈, —CR₅R₆—PR₇R₈,—CR₅R₆—NR₇R₈, —CR₅R₆(OR₇)(OR₈), —CR₅R₆(OR₇)(NR₈), —CR₅R₆(NR₇)(NR₈),anhydride, acetal and ketal groups, —SO₂R₅, amidine groups, —NR₅C(S)NR₆,—NR₅C(S)—OR₆, —N═C═S, —NO₂, —C═N—OH, —N(R₅)═NR₆, —PR₅R₆R₇, —OSiR₅R₆R₇and —SiR₅R₆R₇, where R₅ to R₁₀, independently of one another in eachcase, are defined in the same way as R₁ to R₄, or two of the radicals R₁to R₄ form a C₄- to C₇-ring which in turn may be substituted orunsubstituted and, if required, may contain one or more heteroatom, withthe proviso that at least two of the radicals R₁ to R₃ are aradical-stabilizing and/or bulky group as defined above, or a polymer(B) which is prepared by a process comprising the stage (ii): (ii)Reaction of the reaction product (A) obtained in stage (i), under freeradical conditions, in the presence of at least one monomer (b) capableof free radical homopolymerization or copolymerization, or a mixtureof(A) and (B).
 14. The dispersion as claimed in claim 13, wherein theradical of the formula (III) is derived from at least one compound ofthe formula (I)

where R₁ to R₄, in each case independently of one another, are hydrogen,methyl or a radical-stabilizing and/or bulky group selected from thegroup consisting of unsubstituted and substituted, linear and branchedalkyl groups having two or more carbon atoms, cycloalkyl, alcohol,ether, polyether, amine and aralkyl radicals, a substituted andunsubstituted aromatic, heterocyclic and olefinic hydrocarbons, ahalogen atoms, a substituted and unsubstituted, linear and branchedalkenyl and alkynyl groups, —C(O)R₅, —C(O)OR₅, —CR₅R₆—O—R₇, —O—C(O)R₅,—CN, —O—CN, —S—CN, —O—C═NR₅, —S—C═NR₅, —O—CR₅R₆—CR₇R₈NR₉R₁₀, —N═C═O,—C═NR₅, —CR₅R₆-Hal, —C(S)R₅, —CR₅R₆—P(O)R₇R₈, —CR₅R₆—PR₇R₈,—CR₅R₆—NR₇R₈, —CR₅R₆(OR₇)(OR₈), —CR₅R₆(OR₇)(NR₈), —CR₅R₆(NR₇)(NR₈),anhydride, acetal and ketal groups, —SO₂R₅, amidine groups, —NR₅C(S)NR₆,—NR₅C(S)—OR₆, —N═C═S, —NO₂, —C═N—OH, —N(R₅)═NR₆, —PR₅R₆R₇, —OSiR₅R₆R₇and —SiR₅R₆R₇, where R₅ to R₁₀, independently of one another in eachcase, are defined in the same way as R₁ to R₄, or two of the radicals R₁to R₄ form a C₄- to C₇-ring which in turn may be substituted orunsubstituted and may contain one or more heteroatoms, with the provisothat at least two of the radicals R₁ to R₄ are a radical-stabilizingand/or bulky group, as defined above, or the compounds arediphenylethylene, dinaphthylethylene,4,4′-vinylidenebis(N,N′-dimethylaniline)4,4′-vinylidenebis(aminobenzene) or cis- and trans-stilbene.
 15. Thedispersion as claimed in claim 13, wherein the radical of the formula(III) is derived from at least one compound of the formula (II):

where R₁ to R₄ and R₁₁ and R₁₂, in each case independently of oneanother, are hydrogen, methyl or a radical-stabilizing and/or bulkygroup selected from the group consiting of unsubstituted andsubstituted, linear and branched alkyl groups having two or more carbonatoms, cycloalkyl, alcohol, ether, polyether, amine and aralkylradicals, substituted and unsubstituted aromatic, heterocyclic andolefinic hydrocarbons, halogen atoms, substituted and unsubstituted,linear and branched alkenyl and alkynyl groups, —C(O)R₅, —C(O)OR₅,—CR₅R₆—O—R₇, —O—C(O)R₅, —CN, —O—CN, —S—CN, —O—C═NR₅, —S—C═NR₅,—O—CR₅R₆—CR₇R₈NR₉R₁₀, —N═C═O, —C═NR₅, —CR₅R₆-Hal, —C(S)R₅,—CR₅R₆—P(O)R₇R₈, —CR₅R₆—PR₇R₈, —CR₅R₆—NR₇R₈, —CR₅R₆(OR₇)(OR₈),—CR₅R₆(OR₇)(NR₈), —CR₅R₆(NR₇)(NR₈), an anhydride, acetal and ketalgroups, —SO₂R₅, an amidine groups, —NR₅C(S)NR₆, —NR₅C(S)—OR₆, —N═C═S,—NO₂, —C═N—OH, —N(R₅)═NR₆, —PR₅R₆R₇, —OSiR₅R₆R₇ and —SiR₅R₆R₇, where R₅to R₁₀, independently of one another in each case, are defined in thesame way as R₁ to R₄, or two of the radicals R₁ to R₄ form a C₄- toC₇-ring which in turn may be substituted or unsubstituted and,optionally, contain one or more heteroatoms, with the proviso that atleast two of the radicals R₁ to R₄ are a radical-stabilizing and/orbulky group, as defined above.
 16. The dispersion as claimed in claim13, the radical of the formula (III) comprising the followingcombinations as radical-stabilizing and/or bulky groups: at least onesubstituted or unsubstituted phenyl and —C(O)R₅; at least onesubstituted or unsubstituted phenyl and —CN; at least one substituted orunsubstituted phenyl and —C(O)OR₅; independently of one another, atleast two substituted or unsubstituted phenyl groups; independently ofone another, at least two —C(O)R₅; and independently of one another, atleast two —CN.
 17. The dispersion as claimed in claim 13, the radical(III) being derived from the following compounds of the formula (I) or(II) or mixtures of two or more thereof:1,1,4,4-tetraphenyl-1,3-butadiene 1,4-bis(2-methylstyryl)benzene1,2,3,4,5-pentaphenyl-1,3-cyclopentadiene1,2,3,4-tetraphenyl-1,3-cyclopentadiene acenaphthylene cis- andtrans-alpha-methylstilbene cis- and trans-4,4′-diphenylstilbene,diphenylethylene, dinaphthylethylene,4,4′-vinylidenebis(N,N′-dimethylaniline),4,4′-vinylidenebis(aminobenzene), cis- and trans-stilbene, trans-trans-and trans-cis- and cis-cis-1,4-diphenyl-1,3-butadienealpha,omega-tetraphenylpolyethyne diphenylfulvene triphenylethenetetraphenylethene 1-cyano-1-phenylethylene;1-alkoxycarbonyl-1-phenylethylene; 1,1-dialkoxycarbonyl-2-ethylethylene;1,1-dialkoxycarbonyl-2-phenylethylene,1,1-dialkoxycarbonyl-2,2-dimethylethylene;1,1-dialkoxycarbonylmethylethylene; 9-methylenexanthene;9-methylenethioxanthene, 9-methylene-10-H-acridine, diphenylethylene,dinaphthylethylene, 4,4′-vinylidenebis(N,N′-dimethylaniline),4,4′-vinylidenebis(aminobenzene), cis- and trans-stilbene,1,2-bis(trimethylsilyloxy)tetraphenylethane (TPSE), diethyl -2,3-dicyano-2,3-di(p-tolyl)succinate, hexaphenylethane, compounds of thestructure (Ph₂CR₁—CR₁(Ph)₂, where Ph is substituted or unsubstitutedphenyl and R₁ is selected from the group consisting of: hydrogen, ethyl,—C₂H₄—, —OC₆H₅, OSi(CH₃)₃, —OH, —OC(O)CH₃, —OCH₃, —CH₃, —CO₂C₂H₅, —CN;—OC(O)CH═CH₂, 1,1,2,2-tetraphenyl-1,2-diphenoxyethane (TPPA);1,1,2,2-tetraphenyl-1,2-bis(trimethylsilyloxy)ethane (TPSA) and1,2,2,2-tetraphenyl-1,2-dicyanoethane (TPCA);1,2-diphenyl-1,2-dicyano-1,2-dimethylethane.
 18. The dispersion asclaimed in claim 13, which is prepared in the presence of a lowmolecular weight base selected from the group consisting of NaOH, KOH,ammonia, diethanolamine, triethanolamine, mono-, di- and triethylamine,dimethylethanolamine and a mixture of two or more thereof.
 19. A methodof applying a coating material comprising a reaction product (A) or amixture of two or more thereof or a polymer (B) as claimed in claim 1,comprising the step of dipping, spraying, knife coating, brushing,roller coating, or pouring in the form of a liquid curtain the coatingmaterial onto a substrate selected from the group consisting of films,sheets, fibers, metal sheets, woven fabrics, shaped articles of metal,glass, wood, paper, plastics, leather, mineral substrates, and compositematerials thereof.
 20. A method for preparing a resin materialcomprising a reaction product (A) or a polymer (B) as claimed in claim7, comprising the step of mixing, optionally subsequent roll-milling andkneading (plasticization) and, optionally, subsequent granulation thereaction product (A) or the polymer (B) with additives and optionallyfurther polymers.
 21. A method for preparing a pigment formulationcomprising a reaction product (A) or a polymer (B) as claimed in claim13 as a dispersant comprising the step of mixing a pigment together withone or more dispersant(s) in the presence of water and predispersing ina suitable apparatus, wherein a mixture is obtained, subsequentlymilling the mixture obtained in a mill in order to establish the desiredpigment particle size distribution, adding further assistants, andfinally preparing the final formulation by adding corresponding amountsof water, optionally one or more humectants, and optionally furtherassistants, mixing and then fixing by means of a filtration apparatuswith fines removal in the range from 10 to 1 μm.
 22. A method forpreparing finishes coating materials, toners, cosmetics, resin material,retention aids for papermaking, solubilizers in pharmaceutical andcosmetic formulations, incrustation inhibitors and/or soil-releasepolymers in detergents, filtration assistants and for protecting andclarifying beverages, disinfectants, elastomeric binders in printingplates, a dispersant, preferably in inkjet pigment formulations, anassistant in a tablet matrix, an assistant in the plasticizing ofconcrete, biodegradable polymers for, for example, materials forimplants, surgical suture materials and garbage bags, water-solubleadhesives, adhesives for floor coverings, thickeners of aqueous orpredominantly aqueous systems, sheets, moldings, foams and fibers,pressure-sensitive adhesive materials, solid or liquid adhesives, forproducing self-cleaning surfaces of articles, as stain inhibitors insolid and liquid formulations, plastics used in automotive construction,in the household sector, for leisure articles, in the production of roadsigns, window profiles, lamp covers, garden furniture, boats,surfboards, toys, in the packaging sector, in the production of massageapparatuses and housings therefor, in the production of medicalequipment, in the production of equipment for information processing andtransmission, in the production of extensive wall elements, in transportcontainers, in housings for electrical equipment, in moldings for theconstruction sector or in grating covers comprising the step of mixing areaction product (A) which is prepared by means of a process comprisingthe following stage (i): (i) Reaction, under free radical conditions, ofa reaction mixture comprising at least one monomer (a), capable of freeradical reaction, in the presence of at least one radical of the formula(III)

 where R₁ to R₃, in each case independently of one another, arehydrogen, methyl or a radical-stabilizing and/or bulky group selectedfrom the group consisting of unsubstituted and substituted, linear andbranched alkyl groups having two or more carbon atoms, cycloalkyl,alcohol, ether, polyether, amine and aralkyl radicals, substituted andunsubstituted aromatic, heterocyclic and olefinic hydrocarbons, halogenatoms, a substituted and unsubstituted, linear and branched alkenyl andalkynyl groups, —C(O)R₅, —C(O)OR₅, —CR₅R₆—O—R₇, —O—C(O)R₅, —CN, —O—CN,—S—CN, —O—C═NR₅, —S—C═NR₅, —O—CR₅R₆—CR₇R₈NR₉R₁₀, —N═C═O, —C═NR₅,—CR₅R₆-Hal, —C(S)R₅, —CR₅R₆—P(O)R₇R₈, —CR₅R₆—PR₇R₈, —CR₅R₆—NR₇R₈,—CR₅R₆(OR₇)(OR₈), —CR₅R₆(OR₇)(NR₈), —CR₅R₆(NR₇)(NR₈), anhydride, acetaland ketal groups, —SO₂R₅, amidine groups, —NR₅C(S)NR₆, —NR₅C(S)—OR₆,—N═C═S, —NO₂, —C═N—OH, —N(R₅)═NR₆, —PR₅R₆R₇, —OSiR₅R₆R₇ and —SiR₅R₆R₇,where R₅ to R₁₀, independently of one another in each case, are definedin the same way as R₁ to R₄, or two of the radicals R₁ to R₄ form a C₄-to C₇-ring which in turn may be substituted or unsubstituted and,optionally, contain one or more heteroatom, with the proviso that atleast two of the radicals R₁ to R₃ are a radical-stabilizing and/orbulky group as defined above or a polymer (B) which is prepared by aprocess comprising the stage (ii): (ii) Reaction of the reaction product(A) obtained in stage (i), under free radical conditions, in thepresence of at least one monomer (b) capable of free radicalhomopolymerization or copolymerization, with suitable additives.
 23. Thecoating materials defined in claim 1, wherein the radical of the formula(III) is generated by cleavage of a compound of formula (I) or (II)

in which R₁ to R₄ and R₁₁ and R₁₂, in each case independently of oneanother, are hydrogen, methyl or a radical-stabilizing and/or bulkygroup defined in claim 8, and at least two of the radicals R¹ to R⁴ informula (I) and and at least two to the radicals R¹ to R⁴ in formula(II) are radical-stabilizing and/or bulky groups.
 24. The resinmaterials defined in claim 7, where the radical of the formula (III) isgenerated by cleavage of a compound of formulae (I) or (II)

in which R₁ to R₄ and R₁₁ and R₁₂, in each case independently of oneanother, are hydrogen, methyl or a radical stabilizing and/or bulkygroup defined in claim 8, and at least two of the radicals R¹ to R⁴ informula (I) and and at least two of the radicals R¹ to R⁴ in formula(II) are radical-stabilizing and/or bulky groups.
 25. The aqueousdispersion defined in claim 13, wherein the radical of the formula (III)is generated by cleavage of a compound of formulae (I) or (II)

in which R₁ to R₄ and R₁₁ and R₁₂, in each case independently of oneanother, are hydrogen, methyl or a radical-stabilizing and/or bulkygroup defined in claim 8, and at least two of the radicals R¹ to R⁴ informula (I) and and at least two to the radicals R¹ to R⁴ in formula(II) are radical-stabilizing and/or bulky groups.